EP0692016B1 - Composition d'enzyme pour produits de lavage et de nettoyage - Google Patents

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

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Publication number
EP0692016B1
EP0692016B1 EP94912528A EP94912528A EP0692016B1 EP 0692016 B1 EP0692016 B1 EP 0692016B1 EP 94912528 A EP94912528 A EP 94912528A EP 94912528 A EP94912528 A EP 94912528A EP 0692016 B1 EP0692016 B1 EP 0692016B1
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EP
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Prior art keywords
weight
enzyme
granules
enzyme granules
granulation aid
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EP94912528A
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German (de)
English (en)
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EP0692016A1 (fr
Inventor
Kathleen Paatz
Wilfried Rähse
Werner Pichler
Udo Sturm
Horst Upadek
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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 preparation and the use of the granulate in solid washing and cleaning agents.
  • Enzymes are used extensively in washing, auxiliary washing and cleaning agents.
  • the enzymes are usually not used as concentrates, but in mixtures with a dilution and carrier material. If such enzyme preparations are mixed in with conventional detergents, a considerable reduction in the enzyme activity can occur during storage, especially if bleach-active compounds are present.
  • the storage stability of the enzymes can be significantly increased if the enzymes are encased or embedded in the carrier material and then converted into the desired particle shape by extrusion, pressing and marumerization, as described, for example, in German patent DE 16 17 232, German Offenlegungsschrift DT 20 32 768, and the German interpretations DE 21 37 042 and DE 21 37 043.
  • Such enzyme preparations have poor solubility properties. The undissolved particles can get caught in the laundry and contaminate it, or they can be discharged unused into the wastewater.
  • Embedding agents known from German laid-open specification DT 18 03 099 which consist of a mixture of solid acids or acid salts and carbonates or bicarbonates and disintegrate when water is added Although the solvent power, they are very sensitive to moisture and therefore require additional protective measures.
  • Another disadvantage of the aforementioned preparation is the fact that the enzymes can only be processed in the form of dry powders.
  • the fermentation broths usually produced in enzyme production cannot be used in this form, but must be dewatered beforehand.
  • Processes in which only readily soluble carrier materials such as sugar, starch and cellulose ether are used as binders for the production of enzyme preparations are also bound to this requirement.
  • enzyme granules for use in granular detergents and cleaning agents which contain 2% by weight to 20% by weight of enzyme, 10% by weight to 50% by weight of swellable starch, 5% by weight .-% to 50 wt .-% water-soluble organic polymer as a granulating aid, 10 wt .-% to 35 wt .-% cereal and 3 wt .-% to 12 wt .-% water.
  • Such additives enable enzyme processing without major loss of activity and the storage stability of the enzymes in the granules is also satisfactory.
  • sodium carboxymethyl cellulose has the rate of disintegration and dispersion of the granules in cold wash liquors, while the addition of higher molecular weight polyethylene glycol can change this effect in the direction of a higher dissolution rate.
  • the enzyme granules described there do not always have such a high disintegration rate that when they are used in detergents, sufficient enzyme is already present in the washing liquor in the initial phase of machine washing to remove enzymatically removable soiling.
  • the invention relates to an enzyme granulate suitable for incorporation in particular particulate detergents or cleaning agents, containing enzyme and inorganic and / or organic carrier material and carboxymethyl cellulose-containing granulation aid, which is characterized in that it is a granulation aid system made from alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl or alkenyl polyethoxylate contains the proviso that, based in each case on the finished granulate, at least 0.5% by weight of polyethylene glycol with an average molecular weight of less than 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups are present is when more than 2 wt .-% alkali carboxymethyl cellulose is contained.
  • the degree of substitution of carboxymethyl cellulose is to be understood as the number of etherified oxygen atoms bearing a carboxymethyl group per saccharide monomer of cellulose.
  • the degree of substitution at preferably The carboxymethyl celluloses used are in the range from 0.8 to 0.95, since when they are used, particularly solid granules are obtained or smaller amounts are required to achieve a certain granule strength than when using cellulose with a lower degree of substitution.
  • the presence of sodium carboxymethyl cellulose with a degree of substitution of 0.85 to 0.95, even in quantities of 1% by weight, based on the granulate, in the granulating aid system enables the strength of the granules to be achieved which is the same as when double the amount of sodium carboxymethyl cellulose with a degree of substitution of 0 , 65 to 0.75 correspond.
  • a higher throughput through the extruder can be achieved by using the above-mentioned substituted carboxymethyl cellulose in the production of the granules in the extrusion step.
  • the enzyme granules contain 1% by weight to 30% by weight, calculated as dry substance, protease, lipase, amylase and / or cellulase, 70% by weight to 94% by weight of inorganic and / or organic carrier material and 5% by weight to 50% by weight of granulation aid containing carboxymethyl cellulose and the remainder to 100% by weight of water.
  • An enzyme granulate according to the invention preferably contains a mixture containing, in each case based on finished granulate, 0.1 wt.% To 10 wt.%, In particular 0.5 wt.% To 5 wt.% Carboxymethyl cellulose and 0.1 as the granulation aid system %
  • the invention relates to a method for producing such an enzyme granulate with a grain size of 0.1 mm to 2 mm by extrusion an enzyme premix obtained by mixing a concentrated fermentation broth freed from insoluble constituents by microfiltration with the carrier material and the granulating aid, additives, spheronization of the extrudate in a rounding machine, drying and optionally application of a dye or pigment-containing coating, characterized in that the Fermentation broth mixed with an additive which contains a granulation aid system made from alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate with the proviso that, based in each case on the finished granulate, at least 0.5% by weight polyethylene glycol an average molecular weight below 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups are used if more than 2% by weight of alkali carboxymethyl cellulose is contained in the granulation aid system
  • the primary enzymes that can be used are the proteases, lipases, amylases and / or cellulases obtained from microorganisms, such as bacteria or fungi, proteases produced by Bacillus species and their mixtures with lipases being preferred. They are obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738 and European patent application EP 006 638.
  • the process according to the invention can be used particularly advantageously for the formulation of the very active proteases of the so-called second and higher generations, which include, for example, Savinase (R) and enzymes known from international patent application WO 91/2792, their storage-stable incorporation in detergents and cleaning agents often Problems.
  • the invention it is possible to convert the broths of extracellular enzymes obtained in the fermentation processes directly after removal of the insoluble accompanying substances by microfiltration and subsequent concentration by ultrafiltration and, if appropriate, subsequent evaporation in vacuo, into storage-stable, largely odorless granules. The formation of undesirable enzyme dusts and the loss of activity that occurs during additional drying processes are avoided.
  • Enzymes are preferably contained in the granules according to the invention in amounts of 4% by weight to 20% by weight. If the enzyme granulate according to the invention is a protease-containing formulation, the protease activity is preferably 150,000 protease units (PE, determined according to the method described in surfactants 7 (1970), 125) to 350,000 PE, in particular 160,000 PE to 300,000 PE , per gram of enzyme granules.
  • PE protease units
  • all organic or inorganic pulverulent substances which do not destroy or deactivate the enzymes to be granulated or only tolerably little and which are stable under granulation conditions can be used as carrier materials.
  • Such substances include, for example, starch, cereal flour, cellulose powder, alkali alumosilicate, in particular zeolite, layered silicate, for example bentonite or smectite, and water-soluble inorganic or organic salts, for example alkali metal chloride, alkali metal sulfate, alkali metal carbonate or alkali metal acetate, sodium or potassium being the preferred alkali metals.
  • a carrier material mixture of starch swellable in water, cereal flour and optionally cellulose powder and alkali carbonate is preferably used.
  • the starch which is swellable in water is preferably corn starch, rice starch, potato starch or mixtures thereof, the use of corn starch being particularly preferred.
  • Swellable starch is contained in the enzyme granules according to the invention preferably in amounts of 20% by weight to 50% by weight, in particular from 25% by weight to 45% by weight.
  • the sum of the amounts of the swellable starch and the flour is preferably not more than 80% by weight, in particular 32% by weight to 65% by weight.
  • the cereal flour suitable according to the invention is in particular a product which can be produced from wheat, rye, barley or oats or a mixture of these flours, wholemeal flours being preferred.
  • a wholemeal flour is understood in the context of the invention to mean a flour that has not been fully ground, which has been produced from whole, unpeeled grains or at least predominantly consists of such a product, the rest consisting of fully ground flour or starch.
  • Commercial wheat flour qualities, such as Type 450 or Type 550 are preferably used.
  • the use of flour products too Cereals which lead to the aforementioned swellable starches are possible if care is taken to ensure that the flours have been produced from the whole grains.
  • the flour component of the additive mixture is known to achieve a substantial reduction in odor of the enzyme preparation, which far exceeds the reduction in odor by incorporating the same amounts of corresponding starch types.
  • Such cereal flour is contained in the enzyme granules according to the invention preferably in amounts from 10% by weight to 35% by weight, in particular from 15% by weight to 25% by weight.
  • the enzyme granules according to the invention preferably contain 1% by weight to 50% by weight, preferably 5% by weight to 25% by weight of the granulation aid system, the alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate contains.
  • alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and up to 5 wt .-%, in particular 0.5 wt .-% to 3 wt .-% polyethylene glycol and / or alkyl polyethoxylate, it being important that at least 0.5 wt .-%, especially 0.8 wt .-% to 2 wt .-% polyethylene glycol with an average molecular weight below 1000 and / or alkyl polyethoxylate with at least 20 ethoxy groups is present if more than 2 wt .-% alkali carboxymethyl cellulose is contained.
  • Highly substituted carboxymethyl cellulose, with degrees of substitution up to 3, is preferably not contained in the granulation aid system according to the invention.
  • Carboxymethyl celluloses with degrees of substitution below 0.5 are preferably also not contained in the granulation aid system according to the invention.
  • additional cellulose or starch ethers such as carboxymethyl starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding cellulose mixed ethers, gelatin, casein, tragacanth, maltodextrose, sucrose, invert sugar, glucose syrup or other water-soluble or readily dispersible oligomers can also be used as additional constituents of the granulation aid system natural or synthetic origin.
  • Usable synthetic water-soluble polymers are polyacrylates, polymethacrylates, copolymers acrylic acid with maleic acid or compounds containing vinyl groups, also polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinylpyrrolidone.
  • the aforementioned compounds are those with free carboxyl groups, they are normally in the form of their alkali metal salts, in particular their sodium salts.
  • Such additional granulation aids can be contained in the enzyme granules according to the invention in amounts of up to 10% by weight, in particular from 0.5% by weight to 8% by weight.
  • Higher molecular weight polyethylene glycols i.e. those with an average molecular weight above 1000, can be used as synthetic water-soluble polymers with a dust-binding effect, but it is precisely the higher molecular weight polyethylene glycols which surprisingly bring about an undesirable increase in the granule dissolution time required, so that these substances are preferably completely absent in the enzyme granules according to the invention.
  • fermentation broths are preferably used which are freed of insoluble accompanying substances by microfiltration.
  • the microfiltration is preferably carried out as cross-flow microfiltration using porous tubes with micropores larger than 0.1 ⁇ m, flow rates of the concentrate solution of more than 2 m / s and a pressure difference to the permeate side of less than 5 bar, as for example in the European patent application EP 200 032.
  • the microfiltration permeate is then concentrated, preferably by ultrafiltration, if appropriate with subsequent vacuum evaporation.
  • the concentration can, as described in international patent application WO 92/11347, be carried out in such a way that only relatively low dry matter contents of preferably 5% by weight to 50% by weight, in particular 10% by weight up to 40% by weight.
  • the protease content at this stage of the concentrate is preferably 500,000 PU / g to 1,500,000 PU / g, in particular 600,000 PU / g to 1,000,000 PU / g.
  • the concentrate is metered into a suitably previously prepared dry, powdery to granular mixture of the additives described above.
  • the water content of the mixture should be chosen so that it is in the processing with stirring and impact tools Transfer granular particles that are not sticky at room temperature and plastically deform and extrude them when using higher pressures.
  • the free-flowing premix is, in principle, subsequently processed in a kneader and a connected extruder to form a plastic mass, the result of the mechanical processing being the temperature of between 40 ° C. and 60 ° C., in particular 45 ° C. to 55 ° C. can heat.
  • the material leaving the extruder is passed through a perforated disc with a subsequent knock-off knife and is thereby crushed into cylindrical particles of a defined size.
  • the diameter of the bores in the perforated disk is expediently 0.7 mm to 1.6 mm, preferably 0.8 mm to 1.2 mm.
  • the particles present in this form can then be dried and used for later use.
  • the still moist beads are continuously or in batches, preferably using a fluidized bed drying unit, preferably at 35 ° C. to 50 ° C. and in particular at a maximum product temperature of 45 ° C., to a residual moisture content of 4% by weight to 10% % By weight, preferably 5% by weight to 8% by weight, dried.
  • a fluidized bed drying unit preferably at 35 ° C. to 50 ° C. and in particular at a maximum product temperature of 45 ° C.
  • additional substances can be introduced to coat and coat the particles.
  • Suitable coating materials are in particular the film formers among the aforementioned water-soluble organic polymers.
  • dyes or pigments can also be applied to the particles at this stage in order to cover or change any inherent color, which usually results from the enzyme concentrate.
  • Titanium dioxide in particular has proven to be an inert and physiologically harmless pigment, which preferably is introduced in aqueous dispersion.
  • the water supplied via the pigment dispersion or via the polymer solution is removed again when drying is carried out at the same time or is subsequently required again.
  • the enzyme granules are preferably used for the production of solid, in particular particulate washing or cleaning agents, which can be obtained by simply mixing the enzyme granules with other powder components customary in such agents.
  • the enzyme granules preferably have average grain sizes in the range from 0.1 mm to 2 mm, in particular from 0.4 mm to 1.6 mm.
  • any dusty particles with a grain size below 0.1 mm, in particular below 0.4 mm and any coarse particles with a grain size above 2 mm, in particular above 1.6 mm, can be removed and possibly returned to the manufacturing process will.
  • the granules according to the invention preferably contain less than 5% by weight, in particular at most 1% by weight, of particles with grain sizes outside the range from 0.2 mm to 1.6 mm.
  • 10% by weight to 50% by weight of the concentrated fermentation broth is mixed with 70% by weight to 90% by weight of the carrier material and 0.5% by weight to 10% by weight. of the granulation aid system mixed.
  • the carrier material preferably contains 10% by weight to 70% by weight of cereal flour, 10% by weight to 70% by weight of starch which is swellable in water, 3% by weight to 10% by weight of sucrose and up to 10% by weight .-% cellulose powder, each based on finished enzyme granules.
  • the enzyme preparation obtained consists of largely rounded, dust-free particles which generally have a bulk density of about 500 to 900 grams per liter, in particular 650 to 880 grams per liter. Due to the flexible dry matter content of the broths before they are mixed with the additives, their enzyme activity can, particularly when using protease-containing fermentation broths, in the range of preferably 150,000 to 350,000 protease units per gram (PE / g) 160,000 PE / g to 300,000 PE / g.
  • the granules according to the invention are notable for very high storage stability, in particular at temperatures above room temperature and high atmospheric humidity, and for rapid dissolution behavior in the wash liquor.
  • the granules according to the invention preferably release 100% of their enzyme activity in water at 25 ° C. within 3 minutes, in particular within 90 seconds to 2 minutes.
  • a fermentation broth containing biomass was obtained by fermentation of Bacillus licheniformis (ATCC 53926) modified according to the process described in international patent application WO 91/2792 by transforming a gene sequence from Bacillus lentus DSM 5483 analogous to the process given in German patent DE 29 25 427, which obtained contained about 65,000 protease units per gram (PE / g). This was done by decanting. Cross-flow microfiltration, ultrafiltration (separation limit at molecular weight 10,000) and subsequent evaporation in vacuo according to the procedure described in international patent application WO 92/11347 concentrated to a protease content of 700,000 PE / g ( B1 ).
  • the fermenter broth thus concentrated was mixed in a mixer equipped with a rotating impact tool with the additives listed in Table 1 and homogenized in a kneader provided with external cooling.
  • the plastic mass was extruded using an extruder equipped with a perforated disc (hole diameter 0.9 mm) and a rotating knife.
  • extrudates X1 to X3 and X4 and X5 characterized in Table 1 by their composition, in which a perforated disk with a hole diameter of 1.2 mm was used, were obtained according to the invention and for comparison extrudates V1 to V3 , each with lengths of 0, 7 mm to 1 mm, which were deformed and deburred in a spheronization device (Marumerizer®) for a processing time of about 1 minute while simultaneously dusting with powdered calcium carbonate (3% by weight).
  • the material leaving the spheronizer was dried in a fluidized bed dryer at temperatures from 40 ° C. to 45 ° C. within 15 minutes to a water content of 6% by weight.
  • the dissolution time was determined in a measuring apparatus consisting of a temperable, double-walled beaker, an inclined-blade stirrer, a temperature sensor and a conductivity measuring cell with 4 electrodes, which is connected to an x-t recorder via the conductivity measuring device (type LF 537, WTW).
  • 500 ml of water were heated to 20 ° C. in the beaker while stirring.
  • 5.0 g of the enzyme granules were stirred in and the conductivity-time curve was recorded with the recorder.
  • the time in which 90% of the final value (after 15 minutes) is reached corresponds to the dissolution time in Table 2.

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

Claims (14)

  1. Granulat d'enzyme approprié pour être incorporé dans les produits de lavage ou de nettoyage, contenant de l'enzyme et un matériau de support inorganique et/ou organique ainsi qu'un agent auxiliaire de granulation contenant de la carboxyméthylcellulose,
    caractérisé en ce qu'
    il contient un système d'agents auxiliaires de granulation composé de carboxyméthylcellulose alcaline de degré de substitution compris entre 0,5 et 1 et de polyéthylène glycol et/ou de polyéthoxyphénolate d'alkyle ou d'alkényle, dans la mesure où -par rapport au granulat fini respectivement- au moins 0,5 % en poids de polyéthylène glycol d'une masse molaire moyenne inférieure à 1000 et/ou du polyéthoxyphénolate d'alkyle ou d'alkényle comportant au moins 20 groupes éthoxy sont présents, si plus de 2 % en poids de carboxyméthylcellulose alcaline est contenue.
  2. Granulat d'enzyme selon la revendication 1,
    caractérisé en ce qu'
    il contient, calculé en tant que matière sèche, 1 % à 30 % en poids de protéase, de lipase, d'amylase et/ou de cellulase, 70 % à 94 % en poids de matériau de support inorganique et/ou organique et 5 % à 50 % en poids d'agent auxiliaire de granulation contenant de la carboxyméthylcellulose ainsi que de l'eau jusqu'à 100 %.
  3. Granulat d'enzyme selon la revendication 1 ou 2,
    caractérisé en ce qu'
    il contient comme système d'agents auxiliaires de granulation un mélange contenant, respectivement par rapport au granulat fini, 0,1% à 10 % en poids, en particulier 0,5 % à 5 % en poids de carboxyméthylcellulose ainsi que 0,1 % à 4 % en poids de polyéthylène glycol d'une masse molaire moyenne comprise entre 200 et 600. et/ou un polyéthoxylate selon la formule (I),

            R-(OCH2CH2)n-OH     (I)

    dans laquelle R représente un radical alkyle ou alkényle à chaîne droite ou ramifiée comportant jusqu'à 3 doubles liaisons C-C et entre 10 à 22 atomes de carbone et le degré d'éthoxylation n représente un nombre compris entre 20 et 80.
  4. Granulat d'enzyme selon une des revendications 1 à 3,
    caractérisé en ce que
    le matériaux de support contient par rapport au granulat d'enzyme entre 20 % et 50 % en poids, en particulier entre 25 % à 45 % en poids d'amidon gonflable dans l'eau, en particulier de l'amidon de maïs.
  5. Granulat d'enzyme selon une des revendications 1 à 4,
    caractérisé en ce que
    le matériau de support contient 10 % à 35 % en poids, en particulier 15 % à 25 % en poids de farine de céréales, en particulier de la farine de blé, d'orge, de seigle, d'avoine et leurs mélanges, jusqu'à 10 % en poids, en particulier 2 % à 6 % en poids de cellulose, de phyllosilicate de carbonate alcalin, de chlorure alcalin, de sulfate alcalin, ou d'acétate alcalin, et/ou que l'agent auxiliaire de granulation contient en addition jusqu'à 10 % en poids, en particulier 0,5 % à 8 % en poids d'oligomères ou de polymères d'origine naturelle ou synthétique et qui sont solubles dans l'eau ou peuvent y être dispersés.
  6. Granulat d'enzyme selon une des revendications 1 à 5,
    caractérisé en ce qu'
    il contient de la protéase d'une activité comprise entre 150 000 PE et 350 000 PE, en particulier entre 160 000 PE et 300 000 PE par gramme de granulat d'enzyme.
  7. Granulat d'enzyme selon une des revendications 1 à 6,
    caractérisé en ce qu'
    il présente un taille granulométrique moyenne comprise entre 0,1 mm et 2 mm, en particulier entre 0,4 mm et 1,6 mm et contient moins que 5 % en poids de particules de taille granulométrique en dehors du domaine compris entre 0,2 mm et 1,6 mm.
  8. Granulat d'enzyme selon une des revendications 1 à 7,
    caractérisé en ce qu'
    il libère dans l'eau à 25°C 100 % de son activité enzymatique en l'espace de 3 minutes, en particulier en l'espace de 90 secondes à 2 minutes.
  9. Procédé pour la fabrication d'un granulat d'enzyme d'une taille granulométrique entre 0,1 mm et 2 mm approprié pour l'incorporation dans des produits de lavage et de nettoyage, au moyen de l'extrusion d'un prémélange d'enzyme obtenu en mélangeant le bouillon de fermentation, débarrassé de ses constituants insolubles par microfiltration et concentré, avec le matériau de support et l'agent auxiliaire de granulation comme adjuvants, par la mise en forme sphérique de l'extrudat à l'aide d'un appareil arrondissant le granulat, le séchage et le cas échéant l'application d'une enduction contenant du colorant ou du pigment,
    caractérisé en ce que
    l'on mélange le bouillon de fermentation avec un adjuvant qui contient un système d'agents auxiliaires de granulation composé de carboxyméthylcellulose alcaline d'un degré de substitution compris entre 0,5 et 1 et du polyéthylène glycol et/ou du polyéthoxyphénolate d'alkyle dans la mesure où -par rapport au granulat fini respectivement- au moins 0,5 % en poids de polyéthylène glycol d'une masse molaire moyenne inférieure à 1000 et/ou du polyéthoxyphénolate d'alkyle ou d'alkényle comportant au moins 20 groupes éthoxy sont mis en oeuvre si plus de 2 % en poids de carboxyméthylcellulose alcaline est contenue dans le système d'agents auxiliaires de granulation.
  10. Procédé selon la revendication 9,
    caractérisé en ce que
    10 % à 50 % en poids du bouillon de fermentation concentré est mélangé avec 70 % à 90 % en poids de matériau de support et 0,5 % à 10 % en poids du système d'agents auxiliaires de granulation.
  11. Procédé selon la revendication 9 ou 10,
    caractérisé en ce que
    le matériau de support contient, respectivement par rapport au granulat d'enzyme fini, de préférence 10 % à 70 % en poids de farine de céréales, 10 % à 70 % en poids d'amidon gonflable ans l'eau, 3 % à 10 % en poids de saccharose et jusqu'à 10 % en poids de poudre de cellulose.
  12. Procédé selon une des revendication 9 à 11,
    caractérisé en ce que
    l'extrusion est effectuée à l'aide d'une plaque perforée dont les trous présentent un diamètre compris entre 0,7 mm et 1,6 mm.
  13. Procédé selon une des revendication 9 à 11,
    caractérisé en ce que
    après la mise en forme sphérique de l'extrudat, le granulat est séché à des températures comprises entre 35°C et 50°C jusqu'à présenter une teneur en eau de 4 % à 10 % en poids.
  14. Utilisation d'un granulat d'enzyme selon une des revendication 1 à 8 pour la fabrication de produits de lavage et de nettoyage solides, en particulier sous forme de particules.
EP94912528A 1993-03-31 1994-03-23 Composition d'enzyme pour produits de lavage et de nettoyage Expired - Lifetime EP0692016B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4310506A DE4310506A1 (de) 1993-03-31 1993-03-31 Enzymzubereitung für Wasch- und Reinigungsmittel
DE4310506 1993-03-31
PCT/EP1994/000934 WO1994023005A1 (fr) 1993-03-31 1994-03-23 Composition d'enzyme pour produits de lavage et de nettoyage

Publications (2)

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

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

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DE4420730A1 (de) * 1994-06-15 1995-12-21 Henkel Kgaa Verfahren zur Desodorierung und Stabilisierung biotechnologisch gewonnener Wertstoffe und ihrer wäßrigen Zubereitungen
BR9509787A (pt) * 1994-11-18 1997-12-30 Genecor Int Inc Processo para preparar grânulos de enzima recobertos grânulo de enzima recobertos grânulo de enzima recoberto e composição detergente
US5571446A (en) * 1995-07-27 1996-11-05 Diversey Corporation Anionic stabilized enzyme based clean-in-place system
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DE19600018A1 (de) 1996-01-03 1997-07-10 Henkel Kgaa Waschmittel mit bestimmten oxidierten Oligosacchariden
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
WO1997036986A1 (fr) * 1996-04-01 1997-10-09 Henkel Kommanditgesellschaft Auf Aktien Detergents contenant des complexes activateurs a base d'oligoammine pour composes de peroxy
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DE19649375A1 (de) 1996-11-29 1998-06-04 Henkel Kgaa Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
DE19651446A1 (de) 1996-12-11 1998-06-18 Henkel Kgaa Umhüllte Enzymzubereitung mit verbesserter Löslichkeit
DE19713852A1 (de) 1997-04-04 1998-10-08 Henkel Kgaa Aktivatoren für Persauerstoffverbindungen in Wasch- und Reinigungsmitteln
DE19732751A1 (de) 1997-07-30 1999-02-04 Henkel Kgaa Neue Beta-Glucanase aus Bacillus
DE19732750A1 (de) 1997-07-30 1999-02-04 Henkel Kgaa Glucanasehaltiges Reinigungsmittel für harte Oberflächen
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DE19824705A1 (de) 1998-06-03 1999-12-09 Henkel Kgaa Amylase und Protease enthaltende Wasch- und Reinigungsmittel
DE19850100A1 (de) 1998-10-29 2000-05-04 Henkel Kgaa Polymer-Granulate durch Wirbelschichtgranulation
DE19908051A1 (de) 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
CA2417547A1 (fr) 2000-07-28 2003-01-28 Henkel Kommanditgesellschaft Auf Aktien Nouvelle enzyme amylolytique issue de bacillus sp. a 7-7 (dsm 12368) et lessive et agent de nettoyage contenant cette enzyme amylolytique
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DE10163748A1 (de) 2001-12-21 2003-07-17 Henkel Kgaa Neue Glykosylhydrolasen
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DE102005039580A1 (de) 2005-08-19 2007-02-22 Henkel Kgaa Farbschützendes Waschmittel
DE102007016391A1 (de) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Farbschützendes Wasch- oder Reinigungsmittel
DE102007028310A1 (de) 2007-06-20 2008-12-24 Clariant International Ltd. Tensidmischungen mit synergistischen Eigenschaften
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JP5795254B2 (ja) 2008-04-09 2015-10-14 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 金属ヒドラジド錯体化合物の酸化触媒としての使用
EP2302025B1 (fr) 2009-09-08 2016-04-13 The Procter & Gamble Company Composition de détergent pour linge comprenant des particules de cellulose de carboxyméthyle fortement solubles dans l'eau
KR101831472B1 (ko) 2010-06-28 2018-02-22 바스프 에스이 금속 비함유 표백 조성물
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DE102011010818A1 (de) 2011-02-10 2012-08-16 Clariant International Ltd. Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln
DE102014009836B4 (de) 2014-07-03 2017-04-06 Weylchem Wiesbaden Gmbh Natriumsalze sekundärer Alkansulfonate enthaltende Compounds, ihre Herstellung und Verwendung sowie Wasch-, Desinfektion- und Reinigungsmittel enthaltend diese
DE102015217816A1 (de) 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Verwendung hochkonzentrierter Enzymgranulate zur Erhöhung der Lagerstabilität von Enzymen
WO2017076771A1 (fr) 2015-11-03 2017-05-11 Basf Se Catalyseurs de blanchiment
EP3176157A1 (fr) 2015-12-01 2017-06-07 Basf Se Catalyseurs de blanchiment
WO2017186480A1 (fr) 2016-04-26 2017-11-02 Basf Se Composition de blanchiment sans métal
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ATE157394T1 (de) 1997-09-15
WO1994023005A1 (fr) 1994-10-13
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DE4310506A1 (de) 1994-10-06
DE59403879D1 (de) 1997-10-02
EP0692016A1 (fr) 1996-01-17

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