EP0206418A2 - Composition granulaire contenant un agent de blanchiment sec et une enzyme stable - Google Patents

Composition granulaire contenant un agent de blanchiment sec et une enzyme stable Download PDF

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Publication number
EP0206418A2
EP0206418A2 EP86201055A EP86201055A EP0206418A2 EP 0206418 A2 EP0206418 A2 EP 0206418A2 EP 86201055 A EP86201055 A EP 86201055A EP 86201055 A EP86201055 A EP 86201055A EP 0206418 A2 EP0206418 A2 EP 0206418A2
Authority
EP
European Patent Office
Prior art keywords
enzyme
granular composition
granulate
alkaline buffer
buffer salt
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.)
Granted
Application number
EP86201055A
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German (de)
English (en)
Other versions
EP0206418A3 (en
EP0206418B1 (fr
Inventor
Robert William Herdeman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0206418A2 publication Critical patent/EP0206418A2/fr
Publication of EP0206418A3 publication Critical patent/EP0206418A3/en
Application granted granted Critical
Publication of EP0206418B1 publication Critical patent/EP0206418B1/fr
Expired legal-status Critical Current

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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • This invention relates to an improved dry bleach and stable enzyme granular compositions.
  • Enzymes are used in, for example, the starch industry to produce glucose and fructose by means of amylases, amylglucosidases and glucose isomerases.
  • amylases amylglucosidases
  • glucose isomerases In the dairy industry a vast tonnage of rennets is used and in the detergent industry proteases are normally used as additives in the washing powders to impart a better action on proteinaceous stains on the laundry.
  • U.S. Pat. No. 4,106,991 discloses an improved formation for enzyme granulates comprising enzyme, inorganic salts, a granulation binder, and finely divided cellulose fibers as 2-40% by weight of the granulate.
  • a waxy substance can be employed for the granulating agent, or to coat the granulate.
  • peroxyacid bleach granulates are relatively newcomers to the dry commercial laundry detergent and bleach markets.
  • bleach as used herein unless otherwise specified means peroxyacid bleach and the terms “peroxyacid bleach powder” and “peroxyacid bleach granulates” are synonymous unless otherwise specified.
  • enzyme as used hereinafter means raw enzyme, unless otherwise specified.
  • enzyme powder means a mixture os raw enzyme and inorganic salts.
  • This invention relates to an improved dry bleach and stable enzyme granular composition.
  • the enzyme granulate comprises a homogeneous mixture of proteolytic or amylolytic enzyme and alkaline buffer salt.
  • the improved enzyme granulate is stable when mixed with peroxyacid bleach granulates.
  • the enzyme granulate comprises a homogeneous mixture of proteolytic or amylolytic enzyme and alkaline buffer salt.
  • the improved enzyme granulate is stable when mixed with peroxyacid bleach granulates.
  • granular as used herein means the composition comprising: (1) enzyme granulates and (2) peroxyacid bleach granulates, unless otherwise specified.
  • This invention has an improved water-soluble enzyme granulate containing enzymes, fillers and/or binders and an effective amount of alkaline buffer salt to protect the enzyme from deactivation via contact with peroxyacid bleach granulate.
  • the alkaline buffer salt has a pH of from about 7 to about 11.
  • the practical level of alkali buffer salt material contained in the granulate is from about 3% to about 97.5% by weight of the enzyme granulate.
  • An alkaline buffer salt material as used herein is defined as a material having an effective amount of alkaline buffer salt and compatible inorganic salts.
  • Some practical ratio levels of raw (proteolytic and/or amylase) enzyme to alkaline buffer salt material are from 1:4 to 1:200, preferably 1:6 to 1:100, and more preferably 1:20 to 1:50.
  • the improved enzyme granulate on a weight percentage basis preferably comprises:
  • weight percentages used herein refer to the weight of the granulate being discussed, unless otherwise specified.
  • the improved enzyme granulate preferably is made with a raw enzyme level of from about 0.5% to about 20% (0.25 to 10 Au/gram), and more preferably from about 1% to about 10% (0.5 to 5 Au/gram) by weight of the total composition.
  • Au equals Anson units and is a term commonly used in the trade to describe enzyme activity.
  • the filler and binder in the enzyme granulate can have a ratio of from 10:1 to 1:1.
  • a practical level of cellulosic fillers in the total composition can be from about 2% to about 36%.
  • the stability of the alkaline buffer salt material/enzyme granulate of this invention is further improved with the inclusion of an antioxidant salt to the granulate.
  • the antioxidant is preferably used at a level of from 1% to 40%, more preferably 2% to 30%.
  • the enzyme granulate of this invention is further improved if it has a coating of alkaline buffer salt material including antioxidant with an overcoat of water-soluble nonionic waxy material over said coating.
  • a coating level of at least 10% alkaline buffer salt material by weight of the enzyme granulate is preferred.
  • the waxy overcoat is preferably used at a level of 10% to 30% and more preferably 15% to 25% by weight of said granulate.
  • the improved granular composition of this invention is a mixture of peroxyacid bleach granulates, improved enzyme granulates and, optionally, other laundry active powders including softeners, detergents, etc.
  • powdered detergent materials are disclosed in U.S. Pat. No. 4,404,128, B. J. Anderson, issued Sept. 13, 1983, incorporated herein by reference.
  • detergent composition and builder salts are disclosed in U.S. Pat. No. 3,784,476, van Kampen et al., issued Jan. 8, 1974, incorporated herein by reference.
  • Examples of powdered peroxyacid bleach granulates are disclosed in U.S. Pat. No. 4,473,507, F. P. Bossu, issued Sept. 25, 1984, incorporated herein by reference.
  • Suitable granular compositions can be formulated within the following ranges:
  • a preferred mixture is an enzyme-peroxyacid bleach granular composition
  • a peroxyacid bleach granulate having a weight ratio of from 1:1 to 1:1500 of enzyme granulate to bleach granulate, preferably 1:3 to 1:30. Details of such a preferred mixture is disclosed below.
  • alkaline buffer salt material means a salt having a pH of 7-11 and which provides a comparable pH for the enzyme granulate in the presence of acidic substances for an extended period of time.
  • the alkaline buffer salt material useful in the present invention can include any one of a number of suitable compatible inorganic salts which have a pH of about 7-11. A pH of 8-10 is preferred. The pH of a salt is measured as a 10% solution of the salt.
  • Some preferred alkaline buffer salts are potassium bicarbonate, potassium carbonate, tetrapotassium pyrophosphate, potassium tripolyphosphate, sodium bicarbonate and sodium carbonate. Other suitable alkaline buffer salts can be used.
  • the alkaline buffer salt material can constitute 97.5% of the solids in the enzyme granulate. In this case at least 2% is cellulosic fibers and 0.5% enzyme per Table 1.
  • other compatible materials can be included as part of the alkaline buffer salt material, e.g., other inorganic salts, fillers, binders, etc.
  • Calcium is a preferred component and can be added as calcium sulfate or calcium chloride.
  • antioxidant means a substance that opposes oxidation or inhibits reaction provided by oxygen or peroxides.
  • the antioxidant is an enzyme stability booster for the alkaline buffer salt enzyme granulate.
  • the antioxidant increases the stability of the enzyme when used in conjunction with alkaline buffer salt.
  • the preferred enzyme granulate can contain an antioxidant salt, preferably at a level of from 1-40%, and more preferably 2-30% by weight of the enzyme granulate.
  • Some preferred antioxidant salts are sodium sulfite, sodium bisulfite and sodium thiosulfate. Other suitable antioxidant salts can be used.
  • the enzyme granulate of the present invention has a particle size of from 100 to 1600 preferably from about 200 to about 800 ⁇ , more preferably 300-500 .
  • a preferred process for making enzyme granulates of this invention comprises drum granulating an enzyme material, inorganic salts, a granulation binder, a liquid phase granulating agent, and finely divided cellulose fibers.
  • the inorganic salts are selected to include an effective amount of alkaline buffer salt material to protect the enzyme from rapid deactivation upon exposure to peroxyacid bleach granulates.
  • the process for the production of enzyme granulates comprises the introduction into a drum granulator of from 2 to 40% by weight of cellulose in fibrous form, from 0 to 10% by weight of a binder as herein defined, 0.5% to 20% enzyme and 3% to 97.5% alkaline buffer salt material in an amount which generates the intended enzyme activity in the finished granulate, a liquid phase granulating agent consisting of a waxy substance, as defined herein, and/or water, in an amount of between 5 and 70% by weight, whereby the maximum amount of waxy substance is 40% by weight and the maximum amount of water is 70% by weight, whereby all percentages are referring to the total amount of dry substances, the sequence of the introduction of the different materials being arbitrary, except that at least a major part of the granulating agent is introduced after at least a substantial part of the dry substances is introduced in the granulator, whereafter the granulate, if necessary, is dried in a conventional manner, preferably in a fluid bed.
  • the cellulose in fibrous form can be sawdust, pure, fibrous cellulose, cotton, or other forms of pure or impure fibrous cellulose.
  • Several brands of cellulose in fibrous form are on the market, e.g., CEPO and ARBOCEL.
  • CEPO Chevron Phillips Chemical Company
  • ARBOCEL ARBOCEL
  • CEPO SS/200 cellulose has an approximate maximum fiber length of 15% , an approximate average fiber length of 50 ⁇ , an approximate maximum fiber width of 45 ⁇ and an approximate average fiber width of 25 ⁇ . Cellulose fibers with these dimensions are very well suited for the purpose of the invention.
  • the binders used in the process are the binders conventionally used in the field of granulation with a high melting point or with no melting point at all and of a nonwaxy nature, e.g., polyvinyl pyrrolidone, dextrina, polyvinylalcohol, and cellulose derivatives, including for example hydroxypropyl cellulose, methyl cellulose or CMC.
  • a granulate cannot be formed on the basis of cellulose, filler, enzyme, alkaline buffer salt material and a binder, without the use of a granulating agent, as defined below.
  • enzyme as used herein means raw enzyme unless otherwise specified.
  • the term “enzyme powder” means raw enzyme mixed with inorganic salts such as NaCt, CaCl2,- etc. All enzymes can be granulated by means of said process.
  • amylases and proteinases are granulated according to the invention. Specific examples are ALCALASE (a Bacillus licheniformis proteinase), ESPERASE and SAVINASE (microbial alcaline proteinases produced according to British Pat. No. 1,243,784) and TERMAMYL (a Baccilus licheniformis amylase).
  • the enzyme can be introduced into the granulator as a predried milled powder or as a solution, for example, a concentrated enzyme solution prepared by ultrafiltration, reverse osmosis or evaporation.
  • the granulating agent is water and/or a waxy substance.
  • the granulating agent is always used as a liquid phase in the granulation process; the waxy substance if present therefore is either dissolved or dispersed in the water or melted.
  • a "waxy substance” is understood a “wax” which possesses all of the following characteristics: (1) the melting point is between 30° and 100°C, preferably between 40° and 60°C, (2) the substance is of a tough and not brittle nature, and (3) the substance possesses substantial plasticity at room temperature.
  • Both water and waxy substance are granulating agents, i.e., they are both active during the formation of the granulate; the waxy substance stays as a constituent in the finished granulate, whereas the majority of the water is removed during the drying.
  • all percentages are calculated on the basis of total dry granulate unless otherwise specified, which means that water, one of the granulating agents, is not added to the other constituents when calculating the percentage of water, whereas the waxy substance, the other granulating agent, has to be added to the other dry constituents when calculating the percentage of waxy substance.
  • waxy substances are polyglycols, fatty alcohols, ethoxylated fatty alcohols, higher fatty acids, mono-, di- and triglycerolesters of higher fatty acids, e.g., glycerol monostearate, alkylarylethoxylates, and coconut monoethanolamide.
  • the enzyme granulate produced in the present invention can also be coated with alkaline buffer salt using any number of known apparatuses. Coating in a fluidized bed is preferred. Examples of suitable apparatuses and processes are disclosed in U.S. Pat. Nos. 3,196,827, Wurster and Lindlof, issued July 27, 1965; 3,253,944, Wurster, issued May 31, 1966; and 3,117,027, Lindlof and Wurster, issued Jan. 7, 1964, all incorporated herein by reference.
  • U.S. Pat. No. 3,117,027 discloses a preferred fluidized bed apparatus which can be used for coating the enzyme granulates produced in the present invention.
  • the fluidized bed will provide substantially uniformly enzyme coated granulates.
  • the coating process of the present invention comprises:
  • the protective coating is preferably applied to the enzyme granulate as a 15% to 70% (preferably 20% to 50%) solids aqueous solution in a fluidized bed.
  • the temperature range of the solution can be about 60-82°C (140-1800F), and is preferably about 65-77°C (150-1700F).
  • the air temperature of the fluidized bed is 45° to 77°C for the coating/drying operation.
  • the rate of addition of the coating solution and the rate of drying are dependent on the solution concentration, temperature of air, volume, etc.
  • the enzyme granulate of this invention can be improved if it contains from about 40 to 3000 ppm of calcium calculated as calcium chloride.
  • Calcium can be added to the granulate as calcium chloride or calcium sulfate powder in the granulation process or by using water containing a calcium content of 100-500 ppm, preferably 170-300 ppm, calculated as calcium chloride in the water used in the granulation and/or coating process.
  • a nonionic waxy material can be applied over the enzyme granulate or over the alkaline buffer salt coated enzyme granulate.
  • the practical levels of optional waxy coating material is up to 57% by weight of the composition, preferably 5-30%.
  • waxy coatings are polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, higher fatty acids, mono-, di- and triglycerolesters of fatty acids, e.g., glycerol monostearate, alkylarylethoxylates and coconut monoethanolamide.
  • Preferred nonionic waxy substances are TAE 22 (tallow alcohol condensed with 22 moles of ethylene oxide per mole of alcohol), PEG 1500-8000 (polyethylene glycol of molecular weight 1500-8000) and palmitic acid.
  • Other waxy coatings having a melting point of at least 38°C, preferably at least 50°C, can also be used. For example, this waxy coating is melted (50-70°C) and is sprayed onto the granulate in a fluidized bed where cool air (15-30°C) is applied to solidify the waxy coating.
  • a preferred enzyme granulate can be made using the procedure outlined above using the following ingredients:
  • a 6 inch Wurster Fluidized Bed Coating Unit with a capacity of about 1 liter can be used.
  • the enzyme granulate of Example I can be optionally coated as follows: 800 grams of enzyme granulate are added to the fluid bed dryer. To this a 1 ,000 gram 70°C aqueous solution, containing 200 grams of potassium bicarbonate and 40 grams of sodium sulfite, is sprayed on. The coated enzyme granulate is then dried at a fluid bed temperature of 75°C to contain less than 0.5% water. The coated enzyme granulate is then removed from the fluid bed dryer and weighed to confirm coating level.
  • the ratio of enzyme granulate to protective coating is about 3.3 to 1.
  • the pH of the coating is 8.5.
  • the enzyme granulates similar to that described in Examples I or II are dry mixed with peroxyacid bleach granulates.
  • Example III The process used to make the peroxyacid bleach granulate in Example III is disclosed in U.S. Pat. No. 4,497,757, Beimesch and Hortel, issued Feb. 2, 1985, incorporated herein by reference in its entirety.
  • a detergent powder containing the following components:
  • a laundry additive containing the following components:
  • This invention offers an improved storage stable granular composition
  • an enzyme granulate which is storage stable with a peroxyacid bleach granulate, enabling them to be used together in a detergent or laundry additive product for combined bleaching and stain removal performance.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP19860201055 1985-06-28 1986-06-18 Composition granulaire contenant un agent de blanchiment sec et une enzyme stable Expired EP0206418B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75056985A 1985-06-28 1985-06-28
US750569 1991-08-27

Publications (3)

Publication Number Publication Date
EP0206418A2 true EP0206418A2 (fr) 1986-12-30
EP0206418A3 EP0206418A3 (en) 1988-11-17
EP0206418B1 EP0206418B1 (fr) 1991-11-13

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EP19860201055 Expired EP0206418B1 (fr) 1985-06-28 1986-06-18 Composition granulaire contenant un agent de blanchiment sec et une enzyme stable

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EP (1) EP0206418B1 (fr)
JP (1) JPS6279296A (fr)
AU (1) AU585031B2 (fr)
CA (1) CA1285508C (fr)
DE (1) DE3682443D1 (fr)
GR (1) GR861664B (fr)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0307564A2 (fr) * 1987-09-15 1989-03-22 Ecolab Inc. Méthodes pour introduire des variations de densité de couleur dans des matériaux cellulosiques teints
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
US4865759A (en) * 1985-08-21 1989-09-12 The Clorox Company Dry peracid based bleaching product
EP0396341A2 (fr) * 1989-05-01 1990-11-07 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
US5089167A (en) * 1985-08-21 1992-02-18 The Clorox Company Stable peracid bleaching compositions: organic peracid, magnesium sulfate and controlled amounts of water
US5093021A (en) * 1985-08-21 1992-03-03 The Clorox Company Encapsulated enzyme in dry bleach composition
EP0492679A1 (fr) * 1990-11-26 1992-07-01 Unilever N.V. Poudres détergentes
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
TR25837A (tr) * 1990-05-31 1993-09-01 Procter & Gamble KüLCELENDIRILMIS PEROKSIASIT AGARTICI GRANüLü VE BUNU YAPMAYA MAHSUS YÖNTEM.
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
WO1994010284A1 (fr) * 1992-10-23 1994-05-11 The Procter & Gamble Company Detergents granulaires contenant une enzyme protease et un agent de blanchiment
WO1994026883A2 (fr) * 1993-05-18 1994-11-24 Gist-Brocades N.V. Procede de production d'enzyme exempte de poussiere
WO1995002031A1 (fr) * 1993-07-05 1995-01-19 Henkel Kommanditgesellschaft Auf Aktien Composition enzymatique enrobee pour produits de lavage et de nettoyage
EP0674002A1 (fr) * 1994-03-24 1995-09-27 The Procter & Gamble Company Granules d'enzyme
WO1996000772A1 (fr) * 1994-06-28 1996-01-11 Henkel Kommanditgesellschaft Auf Aktien Granules d'enzymes multiples et leur production
WO1996016151A1 (fr) * 1994-11-18 1996-05-30 Genencor International, Inc. Granules d'enzymes enrobes
EP0723006A2 (fr) * 1995-01-23 1996-07-24 The Procter & Gamble Company Méthodes de nettoyage et produits permettant une libération compatible par étape du produit de blanchiment et des enzymes
EP0780466A1 (fr) * 1995-12-22 1997-06-25 Kao Corporation Produit granulé contenant une enzyme, méthodes pour sa préparation et compositions contenant le granulat
WO1998018899A2 (fr) * 1996-10-26 1998-05-07 Henkel-Ecolab Gmbh & Co. Ohg Procede de fabrication d'agents de lavage et de nettoyage
WO1998026037A2 (fr) * 1996-12-11 1998-06-18 Henkel Kommanditgesellschaft Auf Aktien Preparation d'enzymes enrobes a solubilite amelioree
EP0774504B1 (fr) * 1995-11-17 2003-01-22 Laboratoires ANIOS S.A. Composition pour nettoyer et/ou désinfecter des instruments à usage médical
WO2004003188A2 (fr) * 2002-07-01 2004-01-08 Novozymes A/S Stabilisation de granules
WO2005071054A1 (fr) * 2004-01-09 2005-08-04 Ecolab Inc. Composition de traitement de lessive et procede et appareil de traitement de lessive
US7425528B2 (en) 2002-07-01 2008-09-16 Novozymes A/S Stabilization of granules
EP2674476B1 (fr) 2012-06-11 2018-04-18 The Procter & Gamble Company Composition détergente
US10494591B2 (en) 2017-06-22 2019-12-03 Ecolab Usa Inc. Bleaching using peroxyformic acid and an oxygen catalyst

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL342655A1 (en) * 1997-12-20 2001-07-02 Genencor Int Granule incorporating a hydrated barrier material
US20170260482A1 (en) * 2016-03-08 2017-09-14 The Procter & Gamble Company Particles including enzyme

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NL7000742A (en) * 1970-01-19 1971-07-21 Granular enzyme prepn
FR2357301A1 (fr) * 1976-07-07 1978-02-03 Novo Industri As Procede perfectionne pour la preparation de produits granuleux a base d'enzymes
US4421664A (en) * 1982-06-18 1983-12-20 Economics Laboratory, Inc. Compatible enzyme and oxidant bleaches containing cleaning composition
EP0135227A2 (fr) * 1983-08-15 1985-03-27 Unilever N.V. Compositions pour les machines à laver la vaisselle

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ZA841401B (en) * 1983-03-15 1985-10-30 Colgate Palmolive Co Bleaching and laundering composition free of water-soluble silicates
GB8312185D0 (en) * 1983-05-04 1983-06-08 Unilever Plc Bleaching and cleaning composition

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
NL7000742A (en) * 1970-01-19 1971-07-21 Granular enzyme prepn
FR2357301A1 (fr) * 1976-07-07 1978-02-03 Novo Industri As Procede perfectionne pour la preparation de produits granuleux a base d'enzymes
US4421664A (en) * 1982-06-18 1983-12-20 Economics Laboratory, Inc. Compatible enzyme and oxidant bleaches containing cleaning composition
EP0135227A2 (fr) * 1983-08-15 1985-03-27 Unilever N.V. Compositions pour les machines à laver la vaisselle

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US5093021A (en) * 1985-08-21 1992-03-03 The Clorox Company Encapsulated enzyme in dry bleach composition
US4865759A (en) * 1985-08-21 1989-09-12 The Clorox Company Dry peracid based bleaching product
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
US5089167A (en) * 1985-08-21 1992-02-18 The Clorox Company Stable peracid bleaching compositions: organic peracid, magnesium sulfate and controlled amounts of water
EP0307564B1 (fr) * 1987-09-15 1996-02-21 Ecolab Inc. Méthodes pour introduire des variations de densité de couleur dans des matériaux cellulosiques teints
EP0307564A2 (fr) * 1987-09-15 1989-03-22 Ecolab Inc. Méthodes pour introduire des variations de densité de couleur dans des matériaux cellulosiques teints
EP0396341A2 (fr) * 1989-05-01 1990-11-07 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
EP0396341A3 (fr) * 1989-05-01 1992-01-22 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
TR25837A (tr) * 1990-05-31 1993-09-01 Procter & Gamble KüLCELENDIRILMIS PEROKSIASIT AGARTICI GRANüLü VE BUNU YAPMAYA MAHSUS YÖNTEM.
EP0492679A1 (fr) * 1990-11-26 1992-07-01 Unilever N.V. Poudres détergentes
WO1994010284A1 (fr) * 1992-10-23 1994-05-11 The Procter & Gamble Company Detergents granulaires contenant une enzyme protease et un agent de blanchiment
WO1994026883A2 (fr) * 1993-05-18 1994-11-24 Gist-Brocades N.V. Procede de production d'enzyme exempte de poussiere
WO1994026883A3 (fr) * 1993-05-18 1995-03-02 Gist Brocades Nv Procede de production d'enzyme exempte de poussiere
WO1995002031A1 (fr) * 1993-07-05 1995-01-19 Henkel Kommanditgesellschaft Auf Aktien Composition enzymatique enrobee pour produits de lavage et de nettoyage
US5719115A (en) * 1993-07-05 1998-02-17 Henkel Kommanditgesellschaft Auf Aktien Coated enzyme preparation for detergents and cleaning formulations
CN1046136C (zh) * 1993-07-05 1999-11-03 汉克尔股份两合公司 用于洗涤剂和清洁剂的包复酶制剂
EP0674002A1 (fr) * 1994-03-24 1995-09-27 The Procter & Gamble Company Granules d'enzyme
WO1996000772A1 (fr) * 1994-06-28 1996-01-11 Henkel Kommanditgesellschaft Auf Aktien Granules d'enzymes multiples et leur production
WO1996016151A1 (fr) * 1994-11-18 1996-05-30 Genencor International, Inc. Granules d'enzymes enrobes
EP0723006A2 (fr) * 1995-01-23 1996-07-24 The Procter & Gamble Company Méthodes de nettoyage et produits permettant une libération compatible par étape du produit de blanchiment et des enzymes
EP0723006A3 (fr) * 1995-01-23 1998-07-01 The Procter & Gamble Company Méthodes de nettoyage et produits permettant une libération compatible par étape du produit de blanchiment et des enzymes
EP0774504B1 (fr) * 1995-11-17 2003-01-22 Laboratoires ANIOS S.A. Composition pour nettoyer et/ou désinfecter des instruments à usage médical
EP0780466A1 (fr) * 1995-12-22 1997-06-25 Kao Corporation Produit granulé contenant une enzyme, méthodes pour sa préparation et compositions contenant le granulat
US5858952A (en) * 1995-12-22 1999-01-12 Kao Corporation Enzyme-containing granulated product method of preparation and compositions containing the granulated product
WO1998018899A2 (fr) * 1996-10-26 1998-05-07 Henkel-Ecolab Gmbh & Co. Ohg Procede de fabrication d'agents de lavage et de nettoyage
WO1998018899A3 (fr) * 1996-10-26 1998-07-23 Henkel Ecolab Gmbh & Co Ohg Procede de fabrication d'agents de lavage et de nettoyage
US6350728B1 (en) 1996-12-11 2002-02-26 Henkel Kommanditgesellschaft Auf Aktien (Kgaa) Coated enzyme preparation with an improved solubility
WO1998026037A3 (fr) * 1996-12-11 1998-07-30 Henkel Kgaa Preparation d'enzymes enrobes a solubilite amelioree
WO1998026037A2 (fr) * 1996-12-11 1998-06-18 Henkel Kommanditgesellschaft Auf Aktien Preparation d'enzymes enrobes a solubilite amelioree
WO2004003188A2 (fr) * 2002-07-01 2004-01-08 Novozymes A/S Stabilisation de granules
WO2004003188A3 (fr) * 2002-07-01 2004-02-26 Novozymes As Stabilisation de granules
US7425528B2 (en) 2002-07-01 2008-09-16 Novozymes A/S Stabilization of granules
WO2005071054A1 (fr) * 2004-01-09 2005-08-04 Ecolab Inc. Composition de traitement de lessive et procede et appareil de traitement de lessive
US7682403B2 (en) 2004-01-09 2010-03-23 Ecolab Inc. Method for treating laundry
EP2674476B1 (fr) 2012-06-11 2018-04-18 The Procter & Gamble Company Composition détergente
US10494591B2 (en) 2017-06-22 2019-12-03 Ecolab Usa Inc. Bleaching using peroxyformic acid and an oxygen catalyst

Also Published As

Publication number Publication date
AU5932286A (en) 1987-01-08
AU585031B2 (en) 1989-06-08
CA1285508C (fr) 1991-07-02
DE3682443D1 (de) 1991-12-19
JPS6279296A (ja) 1987-04-11
GR861664B (en) 1986-10-09
EP0206418A3 (en) 1988-11-17
EP0206418B1 (fr) 1991-11-13

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