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WO1991017235A1 - Granules contenant a la fois une enzyme et un agent protecteur d'enzyme, et compositions de detergent contenant lesdits granules - Google Patents

Granules contenant a la fois une enzyme et un agent protecteur d'enzyme, et compositions de detergent contenant lesdits granules Download PDF

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Publication number
WO1991017235A1
WO1991017235A1 PCT/US1991/003044 US9103044W WO9117235A1 WO 1991017235 A1 WO1991017235 A1 WO 1991017235A1 US 9103044 W US9103044 W US 9103044W WO 9117235 A1 WO9117235 A1 WO 9117235A1
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WO
WIPO (PCT)
Prior art keywords
enzyme
granules
detergent
protecting agent
wash medium
Prior art date
Application number
PCT/US1991/003044
Other languages
English (en)
Inventor
Pushkaraj J. Lad
Raymond E. Arnold
David A. Estell
Original Assignee
Genencor International, Inc.
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 Genencor International, Inc. filed Critical Genencor International, Inc.
Publication of WO1991017235A1 publication Critical patent/WO1991017235A1/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
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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 present invention is directed to enzyme granular compositions, to detergent compositions employing such enzyme granular compositions and to methods of retarding the loss of enzyme activity in the detergent wash medium.
  • the enzyme granular compositions employed herein are granules containing both an enzyme and an enzyme protecting agent such as ammonium sulfate.
  • enzymes have been heretofore suggested for use in detergent compositions, e.g., laundry detergent compo- sitions.
  • Such enzymes include proteases, a ylases, Upa ⁇ ses, cellulases, hemicellulases, ⁇ -glycosidases, glucose oxidases, cholesterol oxidases and the like.
  • proteases are generally incorporated into the deter ⁇ gent composition in order to enhance the cleaning ability of the composition against protein stains on the garments being cleaned, e.g., blood, certain foods, etc.
  • lipases are generally incorporated in order to enhance the cleaning ability of the detergent composition against lipid stains, e.g., greases, fats, etc; amylases are generally incorporated in order to enhance the clean- ing ability of the detergent composition against carbohy ⁇ drates; whereas cellulases are generally incorporated in order to enhance the cleaning ability of the detergent composition against plant stains, clays and the like as well to enhance the cleaning capabilities, softening and color restoration of the detergent composition for cotton garments. See, for instance, U.S. Patent Nos. 4,822,516 and 4,443,355.
  • Such composi ⁇ tions generally contain a surfactant and can optionally contain bleaching agents, fluorescent dyes, redeposition preventatives , solubilizing agents and the like. See, for instance. Columns 10 and 11 of U.S. Patent No. 4,822,516. This reference further discloses that agents, such as ammonium sulfate, which act as collectors (scavengers) and reducing agents for effective chlorine found in water can also be incorporated into the deter ⁇ gent composition. In general, the amount of such agents employed in detergent compositions, including scavengers, is that which is sufficient to achieve the desired ef- feet.
  • the present invention is directed to solid granular compositions comprising an enzyme and an enzyme protect ⁇ ing agent.
  • the enzyme protecting agent having one or more enzyme protecting functional groups, provides resistance to loss of enzyme activity when the enzyme is employed in detergent wash media. That is to say that the enzyme protecting agent retards the loss the enzyme activity (i.e., stabilizes the enzyme activity) in deter- gent wash media.
  • the present invention is directed toward a solid" granular composition comprising in granular form, an enzyme and an enzyme protecting agent having one or more enzyme protecting functional groups.
  • the enzyme is incorporated into said granules and even more preferably into the core of the granule whereas the enzyme protecting agent is incorporated into and/or onto said granule.
  • the present inven ⁇ tion is directed toward an enzyme containing detergent composition for use in a detergent wash medium comprising a cleaning effective amount of a surface active agent and granules comprising an enzyme and an enzyme protecting agent.
  • the detergent composition Sufficient amount of granules are employed in the detergent composition so as to ensure that the enzyme will be employed in the detergent wash medium at a con ⁇ centration sufficient for its intended purpose.
  • concentrations are well known to the skilled artisan.
  • the concen ⁇ tration of cellulase in the detergent wash medium will generally range from about 0.1 ppm to about 50,000 ppm; more preferably, from about 1 ppm to about 1,000 ppm; and still more preferably, from about 1 ppm to about 400 ppm.
  • the granules are used in the detergent compo ⁇ sition in an amount of 0.002 to 20 weight percent and preferably 0.1 to 10 weight percent based on the weight of the detergent composition.
  • cellulases produced by microorgan ⁇ isms are multi-enzyme systems and are sometimes referred to herein as "cellulase systems" to distinguish it from the classes and components of cellulase isolated there ⁇ from.
  • classes and components are well known in the art and include exo-cellobiohydrolase components ("CBH components”) , endoglucanase components (“EG components”) , and the like.
  • CBH components and EG components are known in the art to synergistically interact with each other to provide enhanced activity against cellulose.
  • cellulase components can also be used in the detergent compositions. See, in particular. International Applica ⁇ tion, WO 89/09259; U.S. Patent No. 4,822,516 (particular ⁇ ly. Column 3, lines 59-62); U.S. Patent No. 4,435,307; and U.S. Serial No. 07/422,814; and the like, the disclo- sures of which are incorporated herein by reference.
  • hydrolases include carboxylate ester hydrolase, thioester hydrolase, phosphate monoester hydrolase, and phosphate diester hydrolase which act on the ester bond; glycoside hydrolase which acts on glycosyl compounds; an enzyme that hydrolyzes N-glycosyl compounds; thioether hydrolase which acts on the ether bond; and ⁇ -amino-acyl- peptide hydrolase, peptidyl-amino acid hydrolase, acyl- amino acid hydrolase, dipeptide hydrolase, and peptidyl- peptide hydrolase which act on the peptide bond.
  • Suitable hydrolases include (1) proteases belonging to petidyl- peptide hydrolase such as pepsin, pepsin B, rennin, trypsin, chymotrypsin A, chymotrypsin B, elastase, en- terokinase, cathepsin C, papain, chymopapain, ficin, thrombin, fibrinolysin, renin, subtilisin, aspergillopep- tidase A, collagenase, clostridodipep-tidase B, kalli- krein, gastrisin, cathepsin D, bromelin, keratinase, chymotrypsin C, pepsin C, aspergillo-peptidase B, ur
  • ⁇ - amylase and ⁇ -amylase are preferred. They function in acid to neutral systems, but one which is obtained from bacteria exhibits high activity in an alkaline system; (3) carboxylate ester hydrolase including carboxyl esterase, lipase, pectin esterase, and chlorophyllase. Especially effec ⁇ tive among them is lipase.
  • the enzyme protecting agents employed herein refer o those compounds which, when incorporated in the gran- ules at a sufficient concentration, will prevent signifi ⁇ cant loss of enzyme activity over time when these gran ⁇ ules are added to a detergent wash medium.
  • Suitable enzyme protecting agents include ammonium sulfate, urea, guanidine hydrochloride, guanidine carbonate, guanidine sulfamate, thiourea dioxide, monoethanolamine, diethanol- amine, triethanolamine, amino acids such as glycine, sodium glutamate and the like, proteins such as bovine serum albumin, casein, and the like, etc.
  • enzyme protecting agents containing one or more enzyme protecting functional groups selected from the group consisting of amine, ammonium and sulhydryl groups e.g., -NH 3 , -NH 4 + , -SH groups
  • enzyme protecting agents containing one or more enzyme protecting functional groups protect the enzyme from enzymatic activity degradation by offering alterna ⁇ tive sites for oxidation by the oxidizing moieties. That is to say that the presence of a large number of these functionalities in the detergent wash medium will result in enzyme protection because, by shear number of such functionalities, oxidizing agents present in the wash medium will preferentially oxidize these functionalities rather than oxidizing oxidizable functionalities on the enzyme. Accordingly, such functional groups are de ⁇ scribed herein as enzyme protecting functional groups.
  • the concentration of the enzyme protecting agent necessary to impart protection to the enzyme in the detergent wash medium is related to the number of enzyme protecting functional groups present on the protecting agent molecule. That is to say that a smaller quantity of protecting agent containing a high number of enzyme protecting functionalities per molecule is required to provide the same level of protection as compared to protecting agents containing a small number of enzyme protecting functionalities per molecule, (e.g., approximately one-half the quantity of ethane dithiol, HSCH 2 CH 2 SH, is required to achieve the same protecting effect as is achieved by using a full quantity of ethane thiol, CH 3 CH 2 SH) . Accordingly, in the present invention, the relevant criteria for the enzyme protecting agent concentration is, in fact, the concentration of the protecting functionalities which can be defined in terms of the number of mols of such functionalities present.
  • the concentration of the enzyme protect ⁇ ing agent employed is an amount effective to retard the loss of enzymatic activity of the enzyme in the wash me ⁇ dium.
  • the enzyme protecting agent is select- ed so as to provide at least about 1 micromols/liter of the enzyme protecting functional groups, and preferably 40 micromols/liter of the enzyme protecting functional groups, in the detergent wash medium.
  • the concentration of the enzyme protecting agent is selected so as to provide at least about 100 micromols of enzyme protecting functional groups per liter of deter ⁇ gent wash medium, and still even more preferably, at least about 200 micromols of enzyme protecting functional groups per liter of detergent wash medium.
  • the enzyme protecting agents employed herein include some of the same components heretofore employed as chlorine scavengers, the amount or concentration of enzyme protecting agent which imparts improved resistance to loss of enzyme activity in the detergent wash medium is preferably greater than that required to scavenge chlorine. That is to say that such use is an improvement over such previous uses of chlorine scavengers insofar that when used at a higher concentration in the detergent wash medium, these scavengers additionally remove other oxidizing moities which thereby improves the enzymatic activity degradation resistance in the detergent wash medium.
  • the present invention also requires that the enzyme protecting agent be intimately combined with the enzyme in the form of granules.
  • the enzyme protecting agent protects enzyme activity, thereby ensuring that the enzyme will maintain high levels of activity over time in the deter ⁇ gent wash medium.
  • the terms "protect enzyme activity”, “enzyme activity degradation resis ⁇ tance” and “retard the loss of enzyme activity” mean that the loss of enzyme activity in the detergent wash medium is less than that encountered without the use of an enzyme protecting agent.
  • enzyme activity degradation resistance can be measured by comparing the percent loss of enzyme activity in a detergent wash medium with and without the presence of a enzyme protect ⁇ ing agent over the same period of time.
  • the granules of this invention are particularly suited for use in a detergent composition.
  • the granule will generally comprise from about 0.002 to about 20 weight percent and prefera ⁇ bly from about 0.1 to about 10 weight percent of the total detergent composition.
  • the detergent composition will additionally contain a surface active agent, i.e., a surfactant.
  • the surface active agent employed in the detergent composition includes anionic, non-ionic and ampholytic surfactants well known for their use in deter ⁇ gent compositions.
  • Suitable anionic surfactants for use in the deter ⁇ gent composition of this invention include linear or branched alkylbenzenesulfonates; alkyl or alkenyl ether sulfates having linear or branched alkyl groups or alke ⁇ nyl groups; alkyl or alkenyl sulfates; olefinsulfonates; alkanesulfonates and the like.
  • Suitable counter ions for anionic surfactants include alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium and magnesium; ammonium ion; and alkanolamines having 1 to 3 alkanol groups of carbon number 2 or 3.
  • Ampholytic surfactants include quaternary ammonium salt sulfonates, betaine-type ampholytic surfactants, and the like. Such ampholytic surfactants have both the positive and negative charged groups in the same mole ⁇ cule.
  • Nonionic surfactants generally comprise polyoxyalky- lene ethers, as well as higher fatty acid alkanolamides or alkylene oxide adduct thereof, fatty acid glycerine monoesters, and the like.
  • Suitable surfactants for use in this invention are disclosed in British Patent Application No. 2 094 826A, the disclosure of which is incorporated herein by refer ⁇ ence.
  • the detergent compositions of this invention can additionally contain the following components:
  • Cationic surfactants and lon ⁇ -chain fatty acid salts include saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acid salts, ⁇ -sulfo- fatty acid salts or esters, amino acid-type surfactants, phosphate ester surfactants, quaternary ammonium salts including those having 3 to 4 alkyl substituents and up to 1 phenyl substituted alkyl substituents.
  • Suitable cationic surfactants and long-chain fatty acid salts are disclosed in British Patent Application No. 2 094 826 A, the disclosure of which is incorporated herein by refer- ence.
  • the composition may contain from about 1 to about 20 weight percent of such cationic surfactants and long- chain fatty acid salts.
  • the detergent composition may contain from about 0 to about 50 weight percent of one or more builder compo ⁇ nents selected from the group consisting of alkali metal salts and alkanolamine salts of the following compounds: phosphates, phosphonates, phosphonocarboxylates, salts of amino acids, aminopolyacetates high molecular electro ⁇ lytes, non-dissociating polymers, salts of dicarboxylic acids, and aluminosilicate salts, suitable divalent se ⁇ questering agents are disclosed in British Patent Appli- cation No. 2 094 826 A, the disclosure of which is incor ⁇ porated herein by reference. B.
  • builder compo ⁇ nents selected from the group consisting of alkali metal salts and alkanolamine salts of the following compounds: phosphates, phosphonates, phosphonocarboxylates, salts of amino acids, aminopolyacetates high molecular electro ⁇ lytes, non-dissoci
  • the detergent composition may contain from about 1 to about 50 weight percent, preferably from about 5 to about 30 weight percent, based on the composition of one or more alkali metal salts of the following compounds as the alkalis or inorganic electrolytes: silicates, car ⁇ bonates and sulfates as well as organic alkalis such as trietfianolamine, diethanola ine, monoethanolamine and triisopropanolamine.
  • the detergent composition may contain from about 0.1 to about 5 weight percent of one or more of the following compounds as antiredeposition agents: polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and carboxymethylcellulose. mong them, a combination of carboxymethyl-cellulose or/and polyethylene glycol with the cellulase composition of the present invention provides for an especially useful dirt removing composition.
  • carboxymethylcellulose For removing the decomposition of carboxymethyl ⁇ cellulose by the cellulase in the detergent, it is desir ⁇ able that carboxymethylcellulose is granulated or coated before the incorporation in the composition.
  • a bleaching agent such as sodium percar- bonate, sodium perborate, sodium sulfate/hydrogen perox- ide adduct and sodium chloride/hydrogen peroxide adduct or/and a photo-sensitive bleaching dye such as zinc or aluminum salt of sulfonated phthalocyanine further im ⁇ proves the deterging effects.
  • a bleaching agent such as sodium percar- bonate, sodium perborate, sodium sulfate/hydrogen perox- ide adduct and sodium chloride/hydrogen peroxide adduct or/and a photo-sensitive bleaching dye such as zinc or aluminum salt of sulfonated phthalocyanine
  • bluing agents and fluorescent dyes may be incorporated in the composition, if necessary. Suitable bluing agents and fluorescent dyes are disclosed in British Patent Application No. 2 094 826 A, the disclo ⁇ sure of which is incorporated herein by reference.
  • caking inhibitors may be incorporat- ed in the powdery detergent:p-toluenesulfonic acid salts, xylenesulfonic acid salts, acetic acid salts, sulfosuc- cinic acid salts, talc, finely pulverized silica, clay, calcium silicate (such as Micro-Cell of Johns Manville Co.), calcium carbonate and magnesium oxide.
  • Certain enzymes e.g., cellulase
  • Various metal chelating agents and metal-precip ⁇ itating agents are effective against these inhibitors. They include, for example, divalent metal ion sequester ⁇ ing agents as listed in the above item with reference to optional additives as well as magnesium silicate and magnesium sulfate.
  • certain components can act as inhibitors.
  • cellulase it is known that cellobiose, glucose and gluconolactone act sometimes as the inhibitors. It is preferred to avoid the co- presence of these inhibitors with the enzyme as far as possible.
  • co-presence it is necessary to avoid the direct contact of the inhib ⁇ itors with the enzyme by, for example, coating them.
  • Long-chain-fatty acid salts and cationic surfactants can act as the inhibitors of some enzymes, e.g. , cellu ⁇ lase, in some cases.
  • the co-presence of these substances with the enzyme is allowable if the direct contact of them is prevented by some means such as tab- leting or coating.
  • Certain enzymes e.g. cellulase
  • activators vary depending on variety of the cellulases.
  • pro ⁇ teins cobalt and its salts, magnesium and its salts, and calcium and its salts, potassium and its salts, sodium and its salts or monosaccharides such as mannose and xylose
  • the cellulases are activated and their deterging powers are improved remarkably.
  • the antioxidants include, for example, tert-butyl- hydroxytoluene, 4,4'-butylidenebis(6-tert-buty1-3- ethy1- phenol), 2,2'-butylidenebis(6-tert-butyl-4-methylphenol) , monostyrenated cresol, distyrenated cresol, monostyre- nated phenol, distyrenated phenol and l,l-bis(4-hydroxy- phenyl)cyclohexane.
  • the solubilizers include, for example, lower alco ⁇ hols such as ethanol, benzenesulfonate salts, lower alkylbenzenesulfonate salts such as p-toluenesulfonate salts, glycols such as propylene glycol, acetylbenzene- sulfonate salts, acetamides, pyridinedicarboxylic acid amides, benzoate salts and urea.
  • lower alco ⁇ hols such as ethanol, benzenesulfonate salts, lower alkylbenzenesulfonate salts such as p-toluenesulfonate salts, glycols such as propylene glycol, acetylbenzene- sulfonate salts, acetamides, pyridinedicarboxylic acid amides, benzoate salts and urea.
  • the detergent composition of the present invention can be used in a broad pH range of from acidic to alka ⁇ line pH.
  • the detergent composition is em ⁇ ployed in a neutral/alkaline pH and more preferably in a neutral/alkaline pH of from pH 7 to 10.
  • detergent wash medium When the detergent composition is added to an aque ⁇ ous solution so as to produce a cleaning effective con ⁇ centration of a surface active agent, the resulting aqueous solution is sometimes referred to herein as a "detergent wash medium".
  • a detergent base used in the present invention is in the form of a powder, it may be one which is pre ⁇ pared by any known preparation methods including a spray- drying method and a granulation method.
  • the detergent base obtained particularly by the spray-drying method and/or spray-drying granulation method are preferred.
  • the detergent base obtained by the spray-drying method is not restricted with respect to preparation conditions.
  • the detergent base obtained by the spray-drying method is hollow granules which are obtained by spraying an aqueous slurry of heat-resistant ingredients, such as surface active agents and builders, into a hot space.
  • the gran ⁇ ules have a size of from 50 to 2000 micrometers.
  • perfumes, enzymes, bleaching agents, inorganic alkaline builders may be added.
  • various ingredients may also be added after the preparation of the base.
  • the methods of the present invention are carried out by incorporating into a detergent composition the requi ⁇ site amount of the granules of this invention.
  • a detergent composition when such a detergent composition is added to water, the resulting aqueous solution will contain the required amount of the enzyme protecting agent in intimate contact with the enzyme so that immediately upon dissolution, the resulting microenvironment will contain the enzyme and a very high concentration of the enzyme protecting agent so as to protect the enzyme from loss of enzymatic activity over time.
  • enzyme protecting agent in enzyme containing solutions other than detergent wash medium will also result in the pro- tection of the enzyme activity in such media.
  • Such other media include, for instance, industrial enzyme solutions (e.g., cellulase solutions used for food processing, textiles, etc.) and the like.
  • concentration of the enzyme protecting agent necessary to achieve protection of the enzyme activity in such media is as described above for detergent wash media.
  • a 1.05 liter aqueous cellulase concentrate (cellulase available as Cytoclase 123 from Genencor International, 180 Kimball Way, South San Francisco, CA 94080) containing 170 grams/liter protein and 25% total solids is sprayed onto the fluidized cores at a spray rate of about 10 ml/min with an inlet temperature of 45° to 62°C and an outlet temperature of 38° to 46°C.
  • 1466 grams of granules are recovered, repre ⁇ senting a 21.2% weight gain over the non-pariel core.
  • the resulting granules are screened to provide granules between 425 and 1180 microns, a total of 1411 grams.
  • Granule A (706 grams) is then charged into a Uni- Glatt fluidized-bed spray-coater and coated with 37 grams of ammonium sulfate dissolved in 100 mis final volume of deionized water.
  • the ammonium sulfate solution is sprayed onto the fluidized granules at around 10 mls/min with an inlet temperature of 50° to 60 ⁇ C and an outlet temperature of 40° to 46°C.
  • These granules are screened to provide granules between 425 and 1180 microns, a total of 727 grams.
  • the recovery of protein in the 425 to 1180 micron granules is 98.1% of the protein occurring in the Granule A material charged into the fluidized-bed spray- coater.
  • composition contains a sufficient amount of Granule A so as to provide 0.1 weight percent of cellulase (hereinafter "Composition
  • composition B contains a sufficient amount of Granule B so as to provide the same weight percent of cellulase.
  • Composition A and Composition B are added to separate washing machines each of which contains 17 gallons of water at 37°C.
  • a 20 ml aliquot of each solution is withdrawn and the cellulolytic activity is measured, i.e., the zero point measurement. Additional aliquots are withdrawn at 3 minute intervals and the cellulolytic activity is mea ⁇ sured for these samples as well.
  • the cellulolytic activ ⁇ ity of Composition B is significantly higher at all points measured (except for the zero point) .
  • ammonium sulfate other enzymatic protecting agents can be used in place of ammonium sulfate.
  • agents include, for instance, ammonium citrate, urea, guanidine carbonate, guanidine sulfamate, thiourea dioxide, monoethanolamine, diethanol- amine, triethanolamine, amino acids such as glycine, sodium glutamate and the like, proteins such as bovine serum albumin, casein, and the like, etc.
  • Cytolase 123 can be employed in place of Cytolase 123 by merely substituting such other cellu- lase for Cytolase 123 in the above example.
  • commercially available cellulases such as Celluclast (available from Novo Industry, Copenhagen, Denmark) and Rapidase (available from Gist Brocades, N.V. , Delft, Holland) can be used as substitutes for Cytolase 123 in Example 1 above.
  • other enzyme can be employed in place of cellulase by merely substituting such other enzymes for the cellulase in the above example.
  • Such other enzymes include by way of example, proteases, lipases, cutinases, amylases, hemicellulases, /3-glycosidases, glucose oxidases, cholesterol oxidases and the like.

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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)

Abstract

Granulés contenant une enzyme ainsi qu'un agent protecteur d'enzyme. On utilise notamment ces compositions dans des compositions de détergents solides. Lorsqu'on l'utilise ainsi, l'agent protecteur d'enzyme entretient/protège l'activité de l'enzyme lorsque l'on ajoute ladite composition solide à une solution aqueuse de manière à former un milieu de lavage lessiviel.
PCT/US1991/003044 1990-05-04 1991-05-03 Granules contenant a la fois une enzyme et un agent protecteur d'enzyme, et compositions de detergent contenant lesdits granules WO1991017235A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US51845590A 1990-05-04 1990-05-04
US518,455 1990-05-04
US64266991A 1991-01-17 1991-01-17
US642,669 1991-01-17

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WO1991017235A1 true WO1991017235A1 (fr) 1991-11-14

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Cited By (9)

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WO1996035800A1 (fr) * 1995-05-12 1996-11-14 Gist-Brocades B.V. Production enzymatique d'acide gluconique ou de ses sels
EP0745677A1 (fr) * 1995-05-12 1996-12-04 Gist-Brocades B.V. Production enzymatique de l'acide gluconique et de ses sels
FR2739109A1 (fr) * 1995-09-26 1997-03-28 Thor Sarl Produit et procede pour le traitement modificateur de l'etat de surface et/ou de la teinte d'articles textiles
WO2004067739A2 (fr) 2003-01-27 2004-08-12 Novozymes A/S Stabilisation de granules
WO2006066730A1 (fr) * 2004-12-20 2006-06-29 Henkel Kommanditgesellschaft Auf Aktien Procede pour produire des granules enzymatiques presentant une meilleure resistance a l'abrasion
US7425528B2 (en) 2002-07-01 2008-09-16 Novozymes A/S Stabilization of granules
US8043828B2 (en) 2007-01-18 2011-10-25 Danisco Us Inc. Modified endoglucanase II and methods of use
US8772007B2 (en) 2003-12-03 2014-07-08 Danisco Us Inc. Perhydrolase
CN114752653A (zh) * 2022-04-09 2022-07-15 翌圣生物科技(上海)股份有限公司 筛选酶分子稳定剂的方法

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FR2023628A1 (fr) * 1968-11-19 1970-08-21 Procter Gamble Europ
DE1958105A1 (de) * 1969-11-19 1971-05-19 Knapsack Ag Verfahren zur Herstellung enzymhaltiger Granulate
FR2099349A5 (fr) * 1970-07-28 1972-03-10 Novo Terapeutisk Labor As
DE2512044A1 (de) * 1974-03-19 1975-09-25 Unilever Nv Verfahren zur herstellung von granulen mit verminderter neigung zur bildung von staub und nach dem verfahren hergestellte granulen
EP0170360A1 (fr) * 1984-05-29 1986-02-05 Novo Nordisk A/S Granulés contenant des enzymes appropriés pour l'utilisation comme additifs détergents
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FR2023628A1 (fr) * 1968-11-19 1970-08-21 Procter Gamble Europ
DE1958105A1 (de) * 1969-11-19 1971-05-19 Knapsack Ag Verfahren zur Herstellung enzymhaltiger Granulate
FR2099349A5 (fr) * 1970-07-28 1972-03-10 Novo Terapeutisk Labor As
DE2512044A1 (de) * 1974-03-19 1975-09-25 Unilever Nv Verfahren zur herstellung von granulen mit verminderter neigung zur bildung von staub und nach dem verfahren hergestellte granulen
EP0170360A1 (fr) * 1984-05-29 1986-02-05 Novo Nordisk A/S Granulés contenant des enzymes appropriés pour l'utilisation comme additifs détergents
JPS61168698A (ja) * 1985-01-22 1986-07-30 昭和電工株式会社 洗剤用複合酵素粒剤
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WO1996035800A1 (fr) * 1995-05-12 1996-11-14 Gist-Brocades B.V. Production enzymatique d'acide gluconique ou de ses sels
FR2739109A1 (fr) * 1995-09-26 1997-03-28 Thor Sarl Produit et procede pour le traitement modificateur de l'etat de surface et/ou de la teinte d'articles textiles
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