EP0506791B1 - Enzymhaltige zubereitung und eine solche zubereitung enthaltendes detergens - Google Patents
Enzymhaltige zubereitung und eine solche zubereitung enthaltendes detergens Download PDFInfo
- Publication number
- EP0506791B1 EP0506791B1 EP91901708A EP91901708A EP0506791B1 EP 0506791 B1 EP0506791 B1 EP 0506791B1 EP 91901708 A EP91901708 A EP 91901708A EP 91901708 A EP91901708 A EP 91901708A EP 0506791 B1 EP0506791 B1 EP 0506791B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- enzyme
- preparation
- detergent
- savinase
- crystalline
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
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
-
- 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
- C11D3/38663—Stabilised liquid enzyme compositions
Definitions
- the invention encompasses an enzyme containing preparation containing a protease and at least one other enzyme and a detergent containing such preparation.
- preparation means either a granulate or a liquid slurry.
- the slurry can be either anhydrous or substantially anhydrous, or it can be aqueous.
- enzyme containing preparations can be used in different fields, e.g. in the field comprising digestive aids and in the detergent field, but their main use is to be found in the detergent field.
- Enzyme containing granulates are widely used in industry, mainly as dust free additives to detergents.
- protease containing granulates One of the big problems in regard to protease containing granulates is the storage stability of other enzymes present in the granulate. Another big problem in regard to enzyme containing granulates is the storage stability of the enzymes when the enzyme containing granulate is mixed with the other detergent components. Even if several methods for stabilization of the enzymatic activity have been devised, the stability of the enzymatic activity in the enzyme granulate containing detergents is still open to improvement. Another problem in regard to enzyme containing granulates is the color, as most enzyme containing granulates will be discolored, if not coated with e.g. TiO2. A third problem in regard to enzyme containing granulates is the smell thereof. Even after a fairly good purification of the enzyme containing fermentation broth the finished product often exhibits an unagreeable strong smell.
- Anhydrous or substantially anhydrous slurries are widely used in industry, mainly as additives to liquid detergents.
- Aqueous slurries can be used as additives to liquid detergents, in the starch industry and in the food industry. If the slurry is aqueous the water activity or the ionic strenght in the slurry has to be controlled in such manner that the entire amount or substantially the entire amount of the crystalline enzyme is maintained in the crystalline form.
- a big problem in relation to liquid detergents is the stability of enzymes added to these.
- Several stabilization systems have been used in an attempt to overcome this problem. Within the field of low pH formulations both calcium, formate and borate stabilization has been used and are used. Within the higher pH range some of the inhibition methods are also used. But especially within structured liquids a hydrophobic encapsulation has been used, vide Gb 2,186,884A. However, all these stabilization systems are open to improvement.
- Another big problem in regard to liquid, enzyme containing preparations is the color. Most liquid, enzyme containing preparations are colored due to impurities, usually with a dull, brownish color, and also, the color varies somewhat from batch to batch.
- the purpose of the invention is the provision of an enzyme containing preparation, which exhibits an improved stability, and which is colorless or almost colorless and of a high purity, and thus without any smell problems, and a detergent containing such enzyme containing preparation.
- the enzyme containing preparation according to the invention is characterized by the fact that it contains a protease and at least one protease sensitive enzyme, wherein substantially 100% of the proteolytic activity and/or substantially 100% of the protease sensitive enzyme or the protease sensitive enzymes are present as crystals, wherein more than 90% of the crystals possess a maximum crystal dimension between 0.01 ⁇ m and 500 ⁇ m, preferably between 0.1 ⁇ m and 100 ⁇ m, and that the preparation preferably contains a stabilizing agent for the enzymes.
- the stability problems in regard to the protease sensitive enzyme(s) are usually minor.
- the microorganism from which the protease is produced usually differs from the microorganism(s), from which the protease sensitive enzyme(s) is (are) produced, and in such cases serious stability problems may occur.
- the enzyme containing preparation according to the invention it surprisingly has been found that these stability problems are largely eliminated.
- the enzyme containing preparation according to the invention when present in a detergent, possesses an equally good or better enzyme stability than otherwise similar but less pure enzyme containing preparations.
- the protease is Savinase® and the preparation contains the lipase Lipolase® as the other enzyme, and if the preparation is a slurry it has been found that the lipase exhibits an excellent stability.
- the protease sensitive enzyme or the protease sensitive enzymes are present as crystals only a small amount of the protease sensitive enzyme(s) or nothing thereof will be dissolved in the preparation according to the invention, and thus, the stability of the protease sensitive enzyme(s) in the preparation according to the invention will be improved. If the protease is Savinase® and the preparation contains the lipase Lipolase® as the other enzyme, and if the preparation is a granulate it has been found that the lipase exhibits an excellent stability.
- WO 89/08703 describes a method for production of crystalline subtilisin. This crystalline protease could be used as a constituent in the preparation according to the invention. However, WO 89/08703 does not indicate anything about the problems, which arise in relation to the preparations, which besides the crystalline subtilisin contain protease sensitive enzymes.
- the enzyme containing preparations according to the invention can be produced in any conventional manner, if only the conventional enzyme starting material, i.e. enzyme in the form of an amorphous powder, usually with a relatively large amount of impurities, or in the form of an enzyme solution or slurry, is substituted by an enzymatic starting material, in which substantially 100% of the enzymatic activity is present as enzyme crystals.
- the preparation is a granulate, a non limiting list of such usable granulation methods is the previously cited US 4,106,991, US 4,661,452, DOS 2,060,095, and Gb 1,362,365.
- a preferred form of enzyme crystals is described in co-pending patent applications Nos. 847/90 and 848/90 (our refs. 3411.010-DK and 3411.020), filed on the same date as this application.
- Other types of enzyme crystals usable in the enzyme containing preparation are known per se .
- a further advantage in relation to the preparation according to the invention is to be found in the washing process in a washing float with chlorine in the tap water.
- the chlorine will be consumed in the beginning of the washing cycle, and due to the fact that crystalline enzymes are dissolved slower in the washing float than enzymes usually used, the enzymes in the preparation according to the invention will not be present in dissolved form, before part of the chlorine has been consumed, and thus they will be protected from inactivation by the chlorine. Documentation for this will be presented later in this specification.
- the stabilizing agent for the enzymes provides a further improvement of the enzyme stability.
- PVP polyvinyl pyrrolidone
- sucrose and Ca+ + can be used as stabilizing agents.
- crystals possess a maximum crystal dimension between 0.1 ⁇ m and 500 ⁇ m, preferably between 1 ⁇ m and 100 ⁇ m.
- Such crystals are preferably prepared according to co-pending patent applications Nos. 847/90 and 848/90 (our refs. 3411.010-DK and 3411.020-DK), filed on the same date as this application, but they can also be prepared by means of other crystallization methods.
- the protease sensitive enzyme is a lipase, amylase, cellulase, hemicellulase, pectinase, amidase or oxidase, or protein engineered variants of these. These enzymes are common enzymes used as additives in detergents.
- the protease in the preparation according to the invention may be a Subtilisin type protease.
- Examples are Savinase®, Esperase®, Alcalase®, Subtilisin NOVO or protein engineered variants of these. These enzymes are preferred proteases in detergents.
- the protease sensitive enzyme is a lipase and the lipase is Lipolase®.
- the preparation according to the invention may be a granulate. This preparation is well suited as an additive to a detergent in granulate form.
- the preparation according to the invention may be a slurry, which may be anhydrous or substantially anhydrous, or aqueous.
- the preparation according to the invention may be used as a detergent additive. This is the main use of the preparation according to the invention.
- the invention comprises a detergent, which contains the preparation according to the invention, whereby the detergent either is solid and contains the preparation as a granulate in a concentration of between 0.001 and 10 mg of enzyme protein/g of detergent, preferably between 0.005 and 5 mg of enzyme protein/g of detergent, most preferably from 0.01 to 1 mg of enzyme protein/g of detergent, or is liquid and contains the preparation as an anhydrous or substantially anhydrous slurry in an amount of between 0.001 to 10 mg of enzyme protein per g of detergent, preferably from 0.005 to 5 mg of enzyme protein per g of detergent, most preferably from 0.01 to 1 mg of enzyme protein per g of detergent.
- concentrations indicated above will usually be obtained by addition of between 0.01 and 10% w/w of the granulate to the detergent.
- the above indicated liquid detergents exhibit a satisfactory stability of the enzyme.
- binders in relation to the granulate preparations according to the invention is a necessity, and optionally such binders can be carbohydrate binders, e.g. dextrins or cellulose derivatives, for instance hydroxypropyl cellulose, methyl cellulose or CMC.
- carbohydrate binders e.g. dextrins or cellulose derivatives, for instance hydroxypropyl cellulose, methyl cellulose or CMC.
- Savinase® is an alkaline Bacillus protease prepared as indicated in US patent No. 3,723,250. Also, reference can be made to the product sheet for Savinase®, B345 b-GB, March 1988, obtainable from Novo Nordisk A/S on request.
- the KNPU proteolytic activity unit is defined in AF 101.10, which on request can be obtained from Novo Nordisk A/S, Denmark.
- the granulate is finally sifted to get a product with the particle range 300 ⁇ m to 1000 ⁇ m and coated with 7% of PEG 4000 and 12% of a 1:1 mixture of TiO2 and kaolin in a manner as described in US patent No. 4, 106,991, Example 22.
- the mixed dry components are sprayed with 3.6 kg of water. During and after the spraying the moist mixture is exposed to a compacting and granulation influence from the multiple set of knives, as descibed in Example 1 of US patent no. 4,106,991.
- the granulate is dried in a fluid bed, and the part thereof defined as product fraction (in this cae 300-900 ⁇ m) is separated for quality testing.
- product fraction in this cae 300-900 ⁇ m
- the color is measured according to the Hunter Lab Scale (AF 78):
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 2.1 kg of carbohydrate binder 0.63 kg of amorphous Lipolase® 9.7 kg of ground Na2SO4
- the mixed dry components are sprayed with 3.0 kg of water.
- the product fraction is coated for storage stability testing.
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 2.1 kg of carbohydrate binder 0.32 kg of crystalline Lipolase® 1.84 kg of amorphous Savinase® 10.7 kg of ground Na2SO4
- the mixed dry components are sprayed with 3.3 kg of water.
- the product fraction is coated for storage stability testing.
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 2.1 kg of carbohydrate binder 1.6 kg of amorphous Lipolase® 1.84 kg of amorphous Savinase® 9.7 kg of ground Na2SO4
- the mixed dry components are sprayed with 3.3 kg of water.
- the product fraction is coated for storage stability testing.
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 2.1 kg of carbohydrate binder 1.6 kg of amorphous Lipolase® 11.0 kg of ground Na2SO4
- the mixed dry components are sprayed with 0.7 kg of crystalline Savinase® filter cake produced according to DK patent application no. 847/90 suspended in 2.9 kg of water.
- the product fraction is coated for storage stability testing.
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 2.1 kg of carbohydrate binder 0.32 kg of crystalline Lipolase® 12.2 kg of ground Na2SO4
- the mixed dry components are sprayed with 0.7 kg of crystalline Savinase® filter cake produced according to DK patent application no. 847/90 suspended in 3.0 kg of water.
- the product fraction is coated for storage stability testing.
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 2.4 kg of carbohydrate binder 11.7 kg of ground Na2SO4
- the mixed dry components are sprayed with 1.2 kg of crystalline Savinase® filter cake produced according to DK patent application no. 847/90, suspended in 2.2 kg of water, 0.11 kg of Na2SO4 and 0.2 kg of PVP K30.
- Example 2 Produced according to Example 2 with the following formulation: 0.8 kg of kaolin, Speswhite 3.0 kg of fibrous cellulose, Arbocel BC 200 3.0 kg of amorphous Savinase® concentrate 11.2 kg of ground Na2SO4
- the mixed dry components are sprayed with 1.8 kg of carbohydrate binder, 0.2 kg of PVP K30 in 3.0 kg of water.
- Example 8 crystalline Savinase®
- Example 9 amorphous Savinase®
- Example 2 Produced according to Example 2 with the following formulation: 0.7 kg of bentonite ASB 350 1.0 kg of fibrous cellulose, Arbocel BC 200 0.4 kg of carbohydrate binder 4.3 kg of ground Na2SO4
- the mixed dry components are sprayed with 0.354 kg of crystalline Durazym® filter cake produced according to DK patent application no. 847/90, suspended in 1.5 kg of water, 0.07 kg of PVP K30 and 0.4 kg of carbohydrate binder.
- Example 2 Produced according to Example 2 with the following formulation: 1.5 kg of bentonite ASB 350 3.25 kg of fibrous cellulose, Arbocel BC 200 0.9 kg of carbohydrate binder 7.7 kg of ground Na2SO4 2.0 kg of amorphous Durazym®
- the mixed dry components are sprayed with 2.5 kg of water, 0. 15 kg of PVP K30 and 0.5 kg of carbohydrate binder.
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 1.2 kg of carbohydrate binder 11.9 kg of ground Na2SO4 0.46 kg of dry crystalline Savinase®
- the mixed dry components are sprayed with 2.3 kg of water containing 0.2 kg of PVP K30 and 1.2 kg of carbohydrate binder.
- Example 2 Produced according to Example 2 with the following formulation: 2.0 kg of bentonite ASB 350 3.0 kg of fibrous cellulose, Arbocel BC 200 2.4 kg of carbohydrate binder 11.6 kg of ground Na2SO4
- the mixed dry components are sprayed with 1.5 kg of crystalline Savinase® filter cake produced according to DK patent application no. 847/90, suspended in 2.5 kg of water with 0.1 kg of Na2SO4 and 0.2 kg of PVP K30.
- Example 2 Produced according to Example 2 with the following formulation: 0.8 kg of kaolin, Speswhite 1.8 kg of fibrous cellulose, Arbocel BC 200 2.8 kg of amorphous Savinase® 12.6 kg of ground Na2SO4
- the mixed dry components are sprayed with 1.8 kg of carbohydrate binder, 0.2 kg of PVP K30 in 3.6 kg of water.
- 1% of the granulate is added to a European heavy duty detergent and stored in closed jars at 50°C. The activity is measured after 0, 1, 3 and 7 days and calculated in percent.
- liquid preparation Lipolase® 100L in an amount of 1%, crystalline Savinase in an amount of 0.2% and dissolved Savinase® in an amount of 0.625% was added to NOVO standard liquid detergent with builder with the following composition:
- This example illustrates the storage stability of aqueous and anhydrous Savinase® slurries.
- the aqueous slurry base was 54% (NH4)2SO4 in deionized water.
- the anhydrous slurry base was 305 g of Surfactant T9, 140 g Na2SO4 and 15 g Aerosil 200 which were well mixed and homogenized with an Ultra-Turrax mixer.
- the slurries were incubated at 60°C for 5 days and the residual activities were measured.
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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)
- Cosmetics (AREA)
- Enzymes And Modification Thereof (AREA)
Claims (4)
- Enzymhaltige Zubereitung, gekennzeichnet durch die Tatsache, daß sie eine Protease und wenigstens ein protease-sensitives Enzym enthält, wobei im wesentlichen 100% der proteolytischen Aktivität und/oder im wesentlichen 100% des protease-sensitiven Enzyms oder der protease-sensitiven Enzyme als Kristalle vorliegen, wobei mehr als 90% der Kristalle eine maximale Kristallgröße zwischen 0,01 µm und 500 µm, vorzugsweise zwischen 0,1 µm und 100 µm besitzen, und daß die Zubereitung vorzugsweise ein Stabilisierungsmittel für die Enzyme enthält.
- Zubereitung nach Anspruch 1, gekennzeichnet durch die Tatsache, daß das protease-sensitive Enzym eine Lipase, Amylase, Cellulase, Hemicellulase, Pektinase, Amidase oder Oxidase ist, oder proteintechnologische Varianten derselben.
- Zubereitung nach den Ansprüchen 1-2, gekennzeichnet durch die Tatsache, daß das protease-sensitive Enzym eine Lipase ist und daß die Lipase Lipolase® ist.
- Detergens, gekennzeichnet durch die Tatsache, daß es die Zubereitung nach den Ansprüchen 1-3 enthält und daß das Detergens entweder fest ist und die enzymhaltige Zubereitung als ein Granulat in einer Konzentration von zwischen 0,001 und 10 mg Enzymprotein/g Detergens, vorzugweise zwischen 0,005 und 5 mg Enzymprotein/g Detergens, am bevorzugtesten von 0,01 bis 1 mg Enzymprotein/g Detergens enthält, oder daß das Detergens flüssig ist und die enzymhaltige Zubereitung als eine Aufschlämmung in einer Menge von zwischen 0,001 und 10 mg Enzymprotein pro g Detergens, vorzugsweise von 0,005 bis 5 mg Enzymprotein pro g Detergens, am bevorzugtesten von 0,01 bis 1 mg Enzymprotein pro g Detergens enthält.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK6542/89 | 1989-12-21 | ||
| DK654189A DK654189D0 (da) | 1989-12-21 | 1989-12-21 | Enzymholdigt granulat og detergent, der indeholder et saadant granulat |
| DK6541/89 | 1989-12-21 | ||
| DK654289A DK654289D0 (da) | 1989-12-21 | 1989-12-21 | Flydende, enzymholdigt praeparat og flydende detergent, der indeholder et saadant |
| DK84990A DK84990D0 (da) | 1990-04-05 | 1990-04-05 | Enzymholdigt praeparat og detergent, der indeholder et saadant praeparat |
| DK849/90 | 1990-04-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0506791A1 EP0506791A1 (de) | 1992-10-07 |
| EP0506791B1 true EP0506791B1 (de) | 1993-09-08 |
Family
ID=27220960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91901708A Expired - Lifetime EP0506791B1 (de) | 1989-12-21 | 1990-12-21 | Enzymhaltige zubereitung und eine solche zubereitung enthaltendes detergens |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0506791B1 (de) |
| JP (1) | JPH05502584A (de) |
| AT (1) | ATE94206T1 (de) |
| DE (1) | DE69003253T2 (de) |
| DK (1) | DK0506791T3 (de) |
| ES (1) | ES2044718T3 (de) |
| WO (1) | WO1991009941A1 (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153818B2 (en) | 2000-07-28 | 2006-12-26 | Henkel Kgaa | Amylolytic enzyme extracted from bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme |
| EP3645692A1 (de) * | 2017-06-30 | 2020-05-06 | Novozymes A/S | Enzymschlammzusammensetzung |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK173590D0 (da) * | 1990-06-06 | 1990-07-19 | Novo Nordisk As | Rekombinante terapeutiske lipaser |
| ATE161045T1 (de) * | 1992-08-14 | 1997-12-15 | Genencor Int Gmbh | Neue enzymgranulate |
| CN1071786C (zh) * | 1993-02-26 | 2001-09-26 | 普罗格特-甘布尔公司 | 高活性酶颗粒 |
| EP0628625B1 (de) * | 1993-06-07 | 1999-05-06 | The Procter & Gamble Company | Mit Lipase verträgliche Protease in trockenen konzentrierten Bleichmitteln |
| DE4319908A1 (de) * | 1993-06-16 | 1994-12-22 | Solvay Enzymes Gmbh & Co Kg | Flüssige Enzymzubereitungen |
| GB2287713A (en) * | 1994-03-19 | 1995-09-27 | Procter & Gamble | Detergent composition containing pectic enzyme |
| US5789362A (en) * | 1994-03-29 | 1998-08-04 | The Procter & Gamble Co. | Detergent composition comprising lipoxidase enzymes |
| ES2180645T3 (es) | 1994-06-17 | 2003-02-16 | Genencor Int | Metodo de limpieza basado en composiciones que contienen una enzima capaz de degradar las paredes celulares de las plantas y su uso en metodos de limpieza. |
| DE4422609A1 (de) * | 1994-06-28 | 1996-01-04 | Cognis Bio Umwelt | Mehrenzymgranulat |
| NZ295735A (en) * | 1994-12-28 | 1999-06-29 | Genencor International Indiana | Method for stabilizing enzymes in liquid compositions comprising forming an enzyme in an insoluble form and combining with an agent |
| JP3081534B2 (ja) * | 1995-12-22 | 2000-08-28 | 花王株式会社 | 酵素含有造粒物、その製造法及びこれを含有する組成物 |
| CA2216169C (en) * | 1996-01-31 | 2007-01-23 | Gist-Brocades B.V. | Use of compositions comprising stabilized biologically effective compounds |
| EP1021525A1 (de) | 1997-12-20 | 2000-07-26 | Genencor International, Inc. | In einem wirbelschichtbett hergestelltes matrixgranulat |
| CN1242060C (zh) | 1997-12-20 | 2006-02-15 | 金克克国际有限公司 | 基体颗粒 |
| NZ505298A (en) | 1997-12-20 | 2002-10-25 | Genencor Int | Enzyme (protease) granule formulations with salt hydrate and polymer coating having high solubility and increased stability |
| ES2237209T3 (es) | 1998-10-27 | 2005-07-16 | Genencor International, Inc. | Granulo de matriz. |
| MXPA01004750A (es) | 1998-11-13 | 2005-07-01 | Genencor Int | Granulo de baja densidad de lecho fluidizado. |
| DE60026970T2 (de) | 1999-01-08 | 2006-11-30 | Genencor International, Inc., Palo Alto | Zusammensetzungen mit niedriger dichte und partikeln der diese enthalten |
| DE19922753A1 (de) * | 1999-05-18 | 2000-11-23 | Basf Ag | Enzym-Instantformulierungen für die Tierernährung |
| JP2003514922A (ja) | 1999-10-15 | 2003-04-22 | ジェネンコア インターナショナル インコーポレーテッド | 蛋白質含有顆粒および顆粒配合物 |
| JP4499991B2 (ja) | 2001-04-02 | 2010-07-14 | ジェネンコー・インターナショナル・インク | 粉塵生成の潜在性が減少した顆粒 |
| US8076113B2 (en) | 2001-04-02 | 2011-12-13 | Danisco Us Inc. | Method for producing granules with reduced dust potential comprising an antifoam agent |
| US20050181969A1 (en) | 2004-02-13 | 2005-08-18 | Mort Paul R.Iii | Active containing delivery particle |
| PT1809320E (pt) | 2004-10-14 | 2010-10-25 | Altus Pharmaceuticals Inc | Composições contendo lipase, protease e amilase para o tratamento de insuficiência pancreática |
| DE102006018780A1 (de) * | 2006-04-20 | 2007-10-25 | Henkel Kgaa | Granulat eines sensitiven Wasch- oder Reinigungsmittelinhaltsstoffs |
| JP6615758B2 (ja) * | 2013-12-11 | 2019-12-04 | ノボザイムス アクティーゼルスカブ | 水可溶性フィルム中の酵素粒子の使用 |
| DE102015217816A1 (de) | 2015-09-17 | 2017-03-23 | Henkel Ag & Co. Kgaa | Verwendung hochkonzentrierter Enzymgranulate zur Erhöhung der Lagerstabilität von Enzymen |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL33327A (en) * | 1968-11-29 | 1972-12-29 | Lilly Co Eli | A crystalline combination of l-asparaginase and a metal or ammonium or hydrazinium ion and method for preparing the same |
| DK8502857A (de) * | 1984-06-25 | 1985-12-26 | ||
| US5108457A (en) * | 1986-11-19 | 1992-04-28 | The Clorox Company | Enzymatic peracid bleaching system with modified enzyme |
| DE68919688T2 (de) * | 1988-03-18 | 1995-04-13 | Genencor Int | Verfahren zur kristallisation von subtilisin. |
-
1990
- 1990-12-21 WO PCT/DK1990/000340 patent/WO1991009941A1/en not_active Ceased
- 1990-12-21 DE DE91901708T patent/DE69003253T2/de not_active Expired - Fee Related
- 1990-12-21 AT AT91901708T patent/ATE94206T1/de not_active IP Right Cessation
- 1990-12-21 DK DK91901708.7T patent/DK0506791T3/da active
- 1990-12-21 EP EP91901708A patent/EP0506791B1/de not_active Expired - Lifetime
- 1990-12-21 ES ES91901708T patent/ES2044718T3/es not_active Expired - Lifetime
- 1990-12-21 JP JP3502037A patent/JPH05502584A/ja active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153818B2 (en) | 2000-07-28 | 2006-12-26 | Henkel Kgaa | Amylolytic enzyme extracted from bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme |
| 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 |
| EP3645692A1 (de) * | 2017-06-30 | 2020-05-06 | Novozymes A/S | Enzymschlammzusammensetzung |
| EP3645692B1 (de) * | 2017-06-30 | 2025-12-31 | Novozymes A/S | Enzymschlammzusammensetzung |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2044718T3 (es) | 1994-01-01 |
| DK0506791T3 (da) | 1994-03-21 |
| JPH05502584A (ja) | 1993-05-13 |
| DE69003253D1 (de) | 1993-10-14 |
| DE69003253T2 (de) | 1994-01-20 |
| WO1991009941A1 (en) | 1991-07-11 |
| EP0506791A1 (de) | 1992-10-07 |
| ATE94206T1 (de) | 1993-09-15 |
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