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WO1997019160A1 - Preparation enzymatique contenant un co-adjuvant - Google Patents

Preparation enzymatique contenant un co-adjuvant Download PDF

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Publication number
WO1997019160A1
WO1997019160A1 PCT/EP1996/004920 EP9604920W WO9719160A1 WO 1997019160 A1 WO1997019160 A1 WO 1997019160A1 EP 9604920 W EP9604920 W EP 9604920W WO 9719160 A1 WO9719160 A1 WO 9719160A1
Authority
WO
WIPO (PCT)
Prior art keywords
enzyme
weight
detergents
cleaning agents
extrudate
Prior art date
Application number
PCT/EP1996/004920
Other languages
German (de)
English (en)
Inventor
Albrecht Weiss
Beatrix Kottwitz
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1997019160A1 publication Critical patent/WO1997019160A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to an enzyme granulate containing cobuilder, a process for its preparation and the use of the granulate in solid detergents and cleaning agents
  • Enzymes in particular proteases, are used extensively in detergents, washing aids and cleaning agents.
  • the enzymes are usually not used as concentrates, but in mixtures with a diluent and carrier material. If such enzyme preparations are mixed with conventional detergents, storage can be carried out Significant degradation of the enzyme activity occurs, especially when bleach-active compounds are present.
  • Storage stability may be present be increased if the enzymes are encased in the carrier material or embedded in it and then converted into the desired particle shape by extrusion, pressing and mastication, as for example in the German patent specification DE 16 17 232, the German patent application DT 20 32 768 , and the German specifications DE 21 37 042 and DE 21 37 043.
  • Such enzyme preparations have only poor solubility properties. The undissolved particles can get caught in the goods to be cleaned and contaminate them, or they are transferred unused to the wastewater.
  • 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 dissolution or disintegration rate under operating conditions that the granules disintegrate relatively quickly even during storage and d he 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% %
  • water-soluble organic polymer as granulation 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 also the storage stability of the enzymes in the granules is satisfactory
  • the international patent application WO 94/23005 describes enzyme granules for use in granular detergents and cleaning agents. These granules contain enzyme and inorganic and / or organic carrier material as well as carboxymethyl cellulose-containing granulation aids, the granulation aid system Alkali carboxymethyl cellulose with degrees of substitution from 0.1 to 1 and 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 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 carboxymethyl cellulose is present
  • solubility of the enzyme granulate described in the international patent application WO 94/23005 is increased by the special granulation aid system, which contains solubilizing or dust-binding components and grain-strengthening components in optimized ratios
  • the enzyme granules described in the above-mentioned documents have a satisfactory shelf life, both by optimizing the granulation aids, both of the enzymes and of the granules containing them.
  • the increased shelf life is achieved only by adding components which do not contribute to the washing performance of the agents in which the Granules are incorporated.
  • the invention accordingly relates to an enzyme granulate suitable for incorporation in particular particulate detergents and cleaning agents, containing enzyme and inorganic and / or organic carrier material and, if appropriate Granulation aid, which is characterized in that the granulate contains a cobuilder suitable for the detergent and cleaning agent
  • Cobuilders suitable for the detergents and cleaning agents are, in particular, those compounds which support the action of the builder substances, such as, for example, zeolite, without impairing the enzyme activity and also the washing performance.
  • polymeric polyarboxylates are used as cobuilders, for example obtainable by polymerizing unsaturated acids
  • Oxidized starches such as are described in international patent application WO 93/08251 are also suitable
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120 000 and in particular 50,000 to 100,000
  • terpolymers which contain two unsaturated acids and / or their salts as monomer units and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as third monomer unit
  • the first acidic monomer unit or its salt is derived from a monoethylenically unsaturated C3-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from the (meth) acrylic acid whose salt can be a derivative of a C4-Cs-dicarboxylic acid, preferably a Cj-Cg-dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomer unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol
  • vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example C 1 -C 4 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth ) Acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight, preferably 10 to 30% by weight, vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer unit or its salt can also be a derivative of an alkyl sulfonic acid which is in the 2-position with an alkyl radical, preferably with a C-
  • Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate , particularly preferably acrylic acid or acrylate, 10 to 30% by weight, preferably 15 to 25% by weight of methallyisulfonic acid or methallylsulfonate and, as a third monomer unit, 15 to 40% by weight, preferably 20 to 40% by weight of a carbohydrate
  • a mono-, di-, oligo- or polyaccharide with mono-, di- or oligosaccharides being preferred.
  • Sucrose is particularly preferred.
  • the use of the third monomer unit incorporates predetermined breaking points in the polymer which are responsible for the degradability of the polymer Terpolymers used can be produced by any of the known and customary processes
  • Terpolymers which are either completely or at least partially, in particular to more than 50%, based on the carboxyl groups present, are also preferably used.
  • a completely neutralized terpolymer that is to say from the salts of the monomeric acids, in particular the sodium, is particularly preferred - or potassium salts of the monomeric acids, and vinyl alcohol or a carbohydrate.
  • the terpolymers generally have a relative Molecular mass between 1000 and 200000, preferably between 200 and 50000 and in particular between 3000 and 10000 in They are mostly used in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions.
  • Particularly preferred terpolymers are prepared by a process which in German patent applications DE 42 21 381 and DE 43 00 772 are described
  • the amounts of cobuilders and enzymes contained in the granules according to the invention are usually matched to the properties of the finished washing and cleaning agent and can vary within wide ranges
  • the cobuilders are preferably present in the enzyme granulate according to the invention in an amount of 10 to 70% by weight, particularly preferably 15 to 50% by weight
  • Suitable enzymes for the enzyme granules according to the invention are primarily the proteases, lipases, amylases and / or cellulases obtained from microorganisms, such as bacteria or fungi, with proteases produced by bacillus species and their mixtures with lipases and / or cellulases being preferred They are obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,623,957 and No. 4,264,738 and the European patent application EP 006 638 are described.
  • the process according to the invention can be used particularly advantageously for formulating the very active proteases of the so-called second and higher generations, for example Savinase® and enzymes known from international patent application WO 91/2792 belong, the storage stable incorporation in washing and Cleaning agents often cause problems
  • Enzymes are preferably present in the granules according to the invention in amounts of 1% by weight to 20% by weight, particularly preferably 1% by weight to 10% by weight. If the enzyme granules according to the invention are a protease-containing formulation, the protease activity is preferably 1 000 protease units (PE, determined according to the method described in Tenside 7 (1970), 125) to 250,000 PE, particularly preferably 1,000 PE to 100,000 PE and in particular 5,000 to 20,000 PE, per gram of enzyme granules
  • PE protease units
  • organic or inorganic powdery substances which do not destroy or deactivate the enzymes to be granulated, or which can only be tolerated to a limited extent, and which are stable under granulation conditions, can be used as carrier materials.
  • These substances include, for example, starch, cereal flour, cellulose powder, alkali aluminosilicate, in particular zeolite, layered silicate Example bentonite or smectite synthetic, crystalline layered silicate, for example SKS-6® (commercial product from Hoechst AG, BR Germany) 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 are preferred.
  • a carrier material mixture of starch swellable in water, cereal flour and optionally cellulose powder and alkali carbonate is 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 preferably in amounts of 5 to 50% by weight, in particular 10 contain up to 35% 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% to 65% by weight.
  • the cereal flour is, in particular, a product that can be produced from wheat, rye, barley or oats or a mixture of these flours, wholemeal flours being preferred.
  • Whole-grain flour is understood to mean a flour that is not fully ground and that is produced from whole, unpeeled grains is 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.Flour products of the cereal types leading to the aforementioned swellable starches are also 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 reduces the odor by incorporating the same amounts of appropriate starch types
  • grain flour is contained in the enzyme granules according to the invention preferably in amounts of 10% by weight to 35% by weight, in particular 15% by weight to 25% by weight
  • the preparations according to the invention can, as a further component of the carrier material, preferably 1% by weight to 50% by weight, particularly preferably 5% by weight to 25% by weight, based on the total granulate, of a granulation aid system which contains alkali carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycols and / or alkyl polyethoxylate contained in this granulation aid system, based on the finished enzyme granulate, preferably 0.5% to 5% by weight of alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and to to 3% by weight of polyethylene glycol and / or alkyl polyethoxylate, it being particularly preferred if 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 at least 30 ethoxy groups are present if more than 2% by weight of alkali carboxymethyl cellulose are present
  • cellulose or starch ethers such as carboxymethyl starch, methyl cellulose, Hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding cellulose ether, gelatin, casem, tragacanth, maltodextrose, sucrose, invert sugar, glucose syrup, polyvinyl pyrrolidone or other water-soluble or readily dispersible oligomers or polymers of natural or synthetic origin are used to the extent that the aforementioned compounds are such deals with free carboxyl groups, they are usually in the form of their alkali metal salts, in particular their sodium salts.
  • Such additional granulating aids can be used in the enzyme granules according to the invention in amounts of up to 10% by weight, in particular from 0.5% to 8% by weight.
  • contain its high molecular weight polyethylene glycols ie those with an average molecular weight of more than 1000, can be used as synthetic water-soluble polymers with dust-binding effect, but the high molecular weight polyethylene glycols cause an undesirable increase in the required granulate flow sea time, so that these substances are preferably not contained in the enzyme granules according to the invention
  • Another object of the invention is a method for producing an enzyme granulate suitable for incorporation in detergents and cleaning agents
  • an enzyme granulate is produced by extruding an enzyme-cobuilder premix obtained by mixing an aqueous enzyme preparation, which may be a concentrated fermentation broth, which may have been freed of insoluble constituents beforehand by microfiltration, with cobuilders and inorganic and / or organic carrier material as an additive , Spharontechnisch of the extrudate in a Rondiergerat, drying and application of an outer coating layer
  • the cobuilder is uniformly mixed with enzyme and other constituents in the granulate
  • the enzyme granules can be obtained by extruding one by mixing an aqueous enzyme preparation which, if appropriate, frees any insoluble constituents beforehand by microfiltration.
  • concentrated fermentation broth, and inorganic and / or organic carrier material as an additive enzyme premix optionally spheronization of the extrudate in a rounding machine, drying and application of an outer coating layer, an outer coating layer being applied in a fluidized bed made of extrudate, the 5% by weight % to 95% by weight, based on the coating layer, contains Cobuilder
  • the granules obtained by this process consist of a core and an outer shell, the core containing the enzyme and the outer shell containing the cobuilder
  • a third possible process variant is a combination of the two processes described above.
  • the enzyme granulate obtained consists of a core and an outer shell, the enzyme being in the core and the cobuilder being contained both in the core and in the casing
  • the enzyme granules according to the invention are preferably prepared from fermentation broths which are freed of insoluble accompanying substances, for example 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 described, for example, in European patent application EP 200 032.
  • the microfiltration permeate is then preferably concentrated by ultrafiltration, if appropriate with subsequent vacuum evaporation.
  • the concentration can, as in the international patent application WO 92 / 11347, can be carried out in such a way that only relatively low dry matter contents of preferably 5 to 50% by weight, in particular 10% to 40% by weight, are obtained if fermentation contains proteases
  • the protease content at this level of the concentrate is preferably 500,000 PE / g to 1,500,000 PE / g, in particular 600,000 PE / g to 1,000,000 PE / g. powdery to granular mixture of the above additives metered in.
  • This mixture contains depending on Production method also for the cobuilder
  • the water content of the mixture should be selected so that it can be converted into granular particles that do not adhere at room temperature when processed with Ruhr and percussion tools and plastically deformed and extruded when using higher pressures
  • the neself-capable premix obtained is then, in a known manner, subsequently processed in a kneader and a connected extruder to give a plastic mass which is as homogeneous as possible, the result of the mechanical processing being the temperature at temperatures between 40 ° C. and 60 ° C., in particular 45 ° C. can heat up to 55 ° C.
  • the material leaving the extruder is passed through a perforated disk with a subsequent knock-off knife and thereby crushed to cylindrical-shaped particles of defined size.
  • the diameter of the holes in a perforated disk is expediently 0.7 to 1.6 mm, preferably 0.8 to 1.2 mm
  • the particles present in this form can then be dried and coated with a coating system or fed directly to their later use.However, it has proven to be advantageous to subsequently spheronize the cylindrical particles leaving the extruder and chopper, that is to say they are suitable contraption Rounding and deburring a device can be used for this purpose, which consists of a cylindrical container with stationary, rigid rare walls and a friction plate rotatably mounted on the bottom.
  • the beads are continuously or batchwise, preferably using a fluidized bed drying unit, at supply air temperatures of preferably 35 ° C. to 50 ° C. and in particular at a product temperature of not more than 42 ° C.
  • the desired residual moisture content of, for example, 4% by weight to 10% by weight, in particular 5% by weight to 8% by weight, based on the entire granulate, is dried
  • additional substances can be applied to coat and coat the particles.
  • the cobuilder is optionally applied together with other suitable coating materials.
  • Suitable coating substances 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, so as to mask or change any inherent color that usually results from the enzyme concentrate. Titanium dioxide, which is preferably introduced in an aqueous dispersion, has proven particularly useful as an inert and physiologically harmless pigment.
  • the water fed in via the dispersion from the coating substances or via an optionally present polymer solution is removed again during the drying which is carried out at the same time or is subsequently required again.
  • an enzyme core produced by extrusion which is obtainable by extruding a fermentation broth concentrated by mixing an aqueous enzyme preparation, which may be an insoluble constituent which may have been previously freed from microfiltration, and inorganic and / or organic Carrier material as an additive enzyme premix, mixed with a particulate assembled second enzyme under agglomeration conditions, and the coating containing the cobuilder is then applied or simultaneously, the average particle size of the extrudate core containing the first enzyme preferably being 1.1 to 3 times , in particular is 1.3 to 2 times that of the second or further particulate enzyme.
  • the enzyme in the extrudate core is protease and the enzyme contained in the separately produced, smaller particles which agglomerate onto the extrudate is amylase, lipase, cellulase, oxidase and / or peroxidase.
  • the enzyme granules according to the invention are preferably used for the production of solid, in particular particulate detergents or cleaning agents which can be obtained by simply mixing the cobuilder-containing enzyme granules with other powder components customary in such agents.
  • the enzyme granules preferably have particulate detergents and cleaning agents with average grain sizes in the range from 0.1 mm to 3 mm, in particular 0.4 mm to 1.6 mm
  • 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.
  • the granules according to the invention are distinguished by a very high storage stability, particularly in the case of temperature temperatures above room temperature and high air humidity, as well as 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
  • the fermenter broth concentrated in this way was mixed in a mixer equipped with a rotating impact tool with the additives and cobuilders listed below (Sokalan® CP5 (commercial product from BASF, Germany) and in one with a Kneader provided with external cooling homogenized
  • Sokalan® CP5 commercial product from BASF, Germany
  • Kneader provided with external cooling homogenized
  • the extrusion of the plastic mass was carried out by means of an extruder equipped with a perforated disc (hole diameter 0 9 mm) and a rotating knife.
  • Extrudates were obtained each with lengths of 0.7 mm to 1 mm, which were deformed and deburred in a spheronization device (Marume ⁇ zer®) during a processing time of about 1 minute while simultaneously dusting with powdered calcium carbonate (3% by weight) to form rounded particles leaving the spheronizer was well dried in a fluidized bed dryer at temperatures from 40 ° C to 45 ° C within 15 minutes to a water content of 6% by weight. Subsequent sieving largely removed particles with particle sizes below 0.4 mm and above 1.6 mm, the were returned to the process at the stage of mixing with the aggregates
  • a spheronization device Marume ⁇ zer®
  • the enzyme granules were coated by spraying on an aqueous titanium dioxide pigment suspension during the fluidized-bed drying.
  • the enzyme granules according to the invention were obtained in this way
  • Example 2 The granules obtained in Example 1 contained protease with an activity of 184,800 PE / g Example 2
  • An enzyme granulate was produced as described in Example 1, in which a fermenter broth with a protease content of 90,000 PE / g was used.
  • the granulate had the following composition
  • the granules obtained were coated by spraying on a dispersion of 95% by weight, based on the dispersion, co-builders in 5% by weight, based on the dispersion, of C 12 -C 18 fatty alcohol ethoxylate with 7 ethylene oxide groups.
  • the shell was applied to the granule cores applied in an amount of 50 g coating to 50 g granulate core
  • the granules contained cobuilders in an amount of 47.5% by weight, based on the granules, and protease with an activity of 9,000 PU / g

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

L'invention concerne des granulés enzymatiques pouvant être incorporés à des agents de lavage et de nettoyage. Lesdits granulés contiennent l'enyzme, le matériau support organique et/ou inorganique et éventuellement des agents de granulation. Les granulées sont caractérisés en ce qu'ils contiennent également un composant adapté au lavage et au nettoyage, notamment un co-adjuvant adapté à l'agent de lavage et de nettoyage.
PCT/EP1996/004920 1995-11-20 1996-11-11 Preparation enzymatique contenant un co-adjuvant WO1997019160A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19543197.9 1995-11-20
DE1995143197 DE19543197A1 (de) 1995-11-20 1995-11-20 Cobuilderhaltige Enzymzubereitung

Publications (1)

Publication Number Publication Date
WO1997019160A1 true WO1997019160A1 (fr) 1997-05-29

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PCT/EP1996/004920 WO1997019160A1 (fr) 1995-11-20 1996-11-11 Preparation enzymatique contenant un co-adjuvant

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WO (1) WO1997019160A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1004661A1 (fr) * 1998-11-11 2000-05-31 DALLI-WERKE WÄSCHE- und KÖRPERPFLEGE GmbH & Co. KG Granulé de haute densité, procédé pour sa production, son utilisation en tant que désintégrant pour tablettes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3781228A (en) * 1968-05-31 1973-12-25 Colgate Palmolive Co Laundry product containing enzyme
JPS57165497A (en) * 1981-04-07 1982-10-12 Showa Denko Kk Granulation of enzyme
DE4041752A1 (de) * 1990-12-24 1992-06-25 Henkel Kgaa Enzymzubereitung fuer wasch- und reinigungsmittel
JPH07289259A (ja) * 1994-04-27 1995-11-07 Kao Corp 洗剤用酵素造粒物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3781228A (en) * 1968-05-31 1973-12-25 Colgate Palmolive Co Laundry product containing enzyme
JPS57165497A (en) * 1981-04-07 1982-10-12 Showa Denko Kk Granulation of enzyme
DE4041752A1 (de) * 1990-12-24 1992-06-25 Henkel Kgaa Enzymzubereitung fuer wasch- und reinigungsmittel
WO1992011347A2 (fr) * 1990-12-24 1992-07-09 Henkel Kommanditgesellschaft Auf Aktien Preparation enzymatique pour produits de lavage et de nettoyage
JPH07289259A (ja) * 1994-04-27 1995-11-07 Kao Corp 洗剤用酵素造粒物の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8246, Derwent World Patents Index; Class A97, AN 82-98958E, XP002027857 *
PATENT ABSTRACTS OF JAPAN vol. 95, no. 011 *

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