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EP0206418B1 - 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
EP0206418B1
EP0206418B1 EP19860201055 EP86201055A EP0206418B1 EP 0206418 B1 EP0206418 B1 EP 0206418B1 EP 19860201055 EP19860201055 EP 19860201055 EP 86201055 A EP86201055 A EP 86201055A EP 0206418 B1 EP0206418 B1 EP 0206418B1
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.)
Expired
Application number
EP19860201055
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German (de)
English (en)
Other versions
EP0206418A2 (fr
EP0206418A3 (en
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 of 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 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 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 de-activation via contact with peroxyacid bleach granulate.
  • the alkaline buffer salt has a pH of from 7 to 11.
  • the level of alkali buffer salt material contained in the granulate is from 3% to 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.
  • the used ratios of raw 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:
  • the weight percentages used herein refer to the weight of the granulate being discussed, unless otherwise specified.
  • the improved enzyme granulate is made with a raw enzyme level of from 0.5% to 20% (0.25 to 10 Au/gram), and preferably from 1% to 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 cellulosic filler and binder in the enzyme granulate have a ratio of from 1:1 to 10:1.
  • the level of cellulosic fillers in the total composition is from 2% to 40%, preferably from 2% to 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 and detergents having a weight ratio of from 1:1 to 1:1500 of enzyme granulate to bleach granulate.
  • powdered detergent materials are disclosed in U.S. Pat. No. 4,404,128, B. J. Anderson, issued Sept. 13, 1983.
  • detergent composition and builder salts are disclosed in U.S. Pat. No. 3,784,476, van Kampen et al., issued Jan. 8, 1974.
  • Examples of powdered peroxyacid bleach granulates are disclosed in U.S. Pat. No. 4,473,507, F. P. Bossu, issued Sept. 25, 1984.
  • 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 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 and binders.
  • 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 preferably a particle size of from 100 to 1600 micrometers, more preferably from 200 to 800 micrometers, most preferably 300-500 micrometers.
  • 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 e.g., 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 S/20 cellulose the approximate minimum fiber length is 500 micrometers, the approximate average fiber length is 160 micrometers, the approximate maximum fiber width is 50 micrometers and the approximate average fiber width is 30 micrometers.
  • CEPO SS/200 cellulose has an approximate maximum fiber length of 150 micrometers, an approximate average fiber length of 50 micrometers, an approximate maximum fiber width of 45 micrometers and an approximate average fiber width of 25 micrometers. 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, dextrine, 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 NaCl and, CaCl2. 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 Bacillus 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.
  • 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 e.g.,:
  • 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 60-82°C (140-180°F), and is preferably 65-77°C (150-170°F).
  • 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 and volume.
  • the enzyme granulate of this invention can be improved if it contains from 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 TAE22 (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.
  • 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)
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Claims (23)

  1. Composition granulaire stable au stockage, comprenant :
    (I) un granulé contenant une enzyme, comprenant un mélange homogène de 0,5 à 20 % d'une enzyme brute, 3 à 97,5 % d'un sel tampon alcalin, 2 à 40 % d'une charge cellulosique et d'un liant, cette enzyme ayant une activité de 0,25-10 Au/g et
    (II) un granulé contenant un agent de blanchiment aux peracides,

       les granulés (I) et (II) étant présents selon une proportion pondérale de 1:1 à 1:1500 ;
       où ledit sel tampon alcalin a un pH de 7 à 11, mesuré en solution à 10 % ;
       où ladite enzyme brute et ledit sel tampon alcalin sont présents selon une proportion pondérale de 1:4 à 1:200 ;
       où ladite charge cellulosique et ledit liant dudit granulé (I) sont présents en une proportion pondérale de 1:1 à 10:1.
  2. Composition granulaire selon la revendication 1, dans laquelle ledit sel tampon alcalin est choisi dans le groupe comprenant le bicarbonate de potassium, le carbonate de potassium, le pyrophosphate tétrapotassique, le polyphosphate tripotassique, le bicarbonate de sodium et le carbonate de sodium, de préférence le bicarbonate de potassium.
  3. Composition granulaire selon la revendication 1, dans laquelle ledit sel tampon alcalin comprend un sel minéral anti-oxydant choisi dans le groupe comprenant le sulfite de sodium, le bisulfite de sodium et le thiosulfate de sodium et leurs mélanges, la proportion pondérale dudit anti-oxydant au sel tampon alcalin étant de 10:1 à 1:50.
  4. Composition granulaire selon la revendication 1, 2 ou 3, dans laquelle la proportion pondérale dudit granulé (I) audit granulé (II) est de 1:3 à 1:30, et ledit pH est de 8 à 10, et la proportion pondérale de ladite enzyme brute audit sel tampon alcalin est de 1:6 à 1:100.
  5. Composition granulaire selon la revendication 1, 2 ou 3, dans laquelle la proportion pondérale de ladite enzyme brute audit sel tampon alcalin est de 1:20 à 1:50.
  6. Composition granulaire selon la revendication 1, 2 ou 3, dans laquelle ledit granulé contenant une enzyme est enrobé d'un enrobage protecteur contenant une quantité efficace d'un sel tampon alcalin ayant un pH de 7 à 11 ; ledit enrobage protecteur entourant ledit granulé contenant une enzyme et conférant une meilleure stabilité de l'enzyme en présence dudit granulé contenant un agent de blanchiment aux peracides.
  7. Composition granulaire selon la revendication 6, dans laquelle ledit enrobage protecteur est présent en une quantité de 10 à 67 % en poids par rapport audit granulé contenant une enzyme enrobée.
  8. Composition granulaire selon la revendication 6, dans laquelle ledit enrobage protecteur qui entoure ledit granulé contenant l'enzyme est présent en une quantité de 5 à 80 % en poids par rapport audit granulé contenant une enzyme enrobée.
  9. Composition granulaire selon la revendication 6, dans laquelle ledit enrobage protecteur contient 50 à 100 % en poids du sel tampon alcalin par rapport audit enrobage protecteur.
  10. Composition granulaire selon la revendication 6, dans laquelle ledit enrobage protecteur contient 50 à 100 % en poids du sel tampon alcalin par rapport audit enrobage protecteur, et dans laquelle ledit sel tampon alcalin est présent en une quantité de 5 à 10 % en poids par rapport audit granulé contenant une enzyme, et dans laquelle le reste dudit enrobage protecteur est choisi parmi les anti-oxydants, le chlorure de calcium et d'autres sels minéraux compatibles.
  11. Composition granulaire selon la revendication 6, dans laquelle ledit enrobage protecteur contenant un sel tampon alcalin a un pH de 8 à 10, la proportion dudit granulé contenant une enzyme et dudit enrobage protecteur étant de 4:1 à 1:1.
  12. Composition granulaire selon la revendication 1, 2 ou 3, dans laquelle l'anti-oxydant est présent en une quantité de 1 à 40 % en poids par rapport audit granulé contenant une enzyme, ledit sel tampon alcalin étant présent en une quantité efficace permettant de stabiliser ladite enzyme contre une rapide désactivation en présence d'un granulé contenant un agent de blanchiment aux peracides.
  13. Composition granulaire selon la revendication 12, dans laquelle ledit anti-oxydant est présent en une quantité de 2 à 30 % en poids par rapport audit granulé contenant une enzyme.
  14. Composition granulaire selon la revendication 6, dans laquelle ledit enrobage protecteur est un mélange du sel tampon alcalin et d'un anti-oxydant, cet enrobage ayant un pH de 8 à 10.
  15. Composition granulaire selon la revendication 6, dans laquelle ledit sel tampon alcalin est choisi dans le groupe comprenant le bicarbonate de potassium, le carbonate de potassium, le pyrophosphate tétrapotassique, le polyphosphate tripotassique,le bicarbonate de sodium et le carbonate de sodium et leurs mélanges, ledit sel tampon alcalin dudit enrobage protecteur étant présent en une quantité de 5 à 50 % en poids par rapport audit granulé contenant une enzyme.
  16. Composition granulaire selon la revendication 1, 2 ou 3, dans laquelle ledit granulé contenant une enzyme contient un ion calcium dérivant du sulfate de calcium ou du chlorure de calcium en une quantité de 40 à 3000 ppm en poids par rapport audit granulé contenant une enzyme, cette quantité étant calculée sous forme de chlorure de calcium.
  17. Composition granulaire selon la revendication 1, 2 ou 3, dans laquelle ledit granulé contenant une enzyme est entouré d'un enrobage constitué d'une cire non-ionique soluble dans l'eau ayant un point de fusion d'au moins 38°C.
  18. Composition granulaire selon la revendication 1, 2 ou 3, dans laquelle ledit granulé contenant une enzyme comprend un enrobage du type cire non ionique, en une quantité de 5 à 57 % en poids par rapport audit granulé contenant une enzyme, et a un point de fusion d'au moins 50°C.
  19. Composition granulaire selon la revendication 18, dans laquelle ledit enrobage constitué d'une cire non ionique soluble dans l'eau est présent en une quantité de 10 à 30 % en poids par rapport audit granulé contenant une enzyme.
  20. Composition granulaire selon la revendication 18, dans laquelle ledit revêtement du type cire non ionique soluble dans l'eau est présent en une quantité de 15 à 25 % en poids par rapport audit granulé contenant une enzyme.
  21. Composition granulaire selon la revendication 17, dans laquelle ladite cire non ionique est choisie dans le groupe comprenant les alcools gras, les alcools gras éthoxylés, les acides gras supérieurs, les esters du mono-, du di-et du triglycérol d'acides gras, par exemple le monostéarate de glycérol, les dérivés alkylaryliques polyéthoxylés et le (huile de coprah)-monoéthanolamide, et leurs mélanges.
  22. Composition granulaire selon la revendication 21, dans laquelle ladite cire non ionique est choisie dans le groupe comprenant le TAE₂₂, le PEG 1500-8000 et les acides palmitiques.
  23. Composition granulaire selon l'une quelconque des revendications précédentes, caractérisée en ce que ledit mélange homogène de l'enzyme brute est un mélange homogène d'enzymes protéolytiques et d'enzymes amylolytiques.
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 1985-06-28

Publications (3)

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

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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)

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US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
ES2001074A6 (es) * 1985-08-21 1988-04-16 Clorox Co Perfeccionamientos en la fabricacion de productos blanqueantes secos basados en diperacidos.
ATE72579T1 (de) * 1985-08-21 1992-02-15 Clorox Co Stabiles persaeurebleichmittel.
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US4832864A (en) * 1987-09-15 1989-05-23 Ecolab Inc. Compositions and methods that introduce variations in color density into cellulosic fabrics, particularly indigo dyed denim
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.
GB9025673D0 (en) * 1990-11-26 1991-01-09 Unilever Plc Detergent powders and process for preparing them
PL175424B1 (pl) * 1992-10-23 1998-12-31 Procter & Gamble Granulowany detergent z enzymem proteolitycznym i środkiem bielącym
EP0675952A1 (fr) * 1993-05-18 1995-10-11 Genencor International, Inc. Procede de production d'enzyme exempte de poussiere
DE4322229A1 (de) * 1993-07-05 1995-01-12 Cognis Bio Umwelt Umhüllte Enzymzubereitung für Wasch- und Reinigungsmittel
DE69428427T2 (de) * 1994-03-24 2002-06-20 The Procter & Gamble Company, Cincinnati Enzymgranulate
DE4422609A1 (de) * 1994-06-28 1996-01-04 Cognis Bio Umwelt Mehrenzymgranulat
JPH10508755A (ja) * 1994-11-18 1998-09-02 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 被覆酵素顆粒
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
FR2741355B1 (fr) * 1995-11-17 1998-12-31 Anios Lab Sarl Composition pour le traitement d'objets que l'on souhaite nettoyer et/ou desinfecter
US5858952A (en) * 1995-12-22 1999-01-12 Kao Corporation Enzyme-containing granulated product method of preparation and compositions containing the granulated product
DE19644591A1 (de) * 1996-10-26 1998-04-30 Henkel Ecolab Gmbh & Co Ohg Verfahren zur Herstellung enzym- und bleichmittelhaltiger Wasch- und Reinigungsmittel
DE19651446A1 (de) 1996-12-11 1998-06-18 Henkel Kgaa Umhüllte Enzymzubereitung mit verbesserter Löslichkeit
BR9813768A (pt) * 1997-12-20 2000-10-10 Genencor Int Grânulo, e, processo de produção de um grânulo.
US7425528B2 (en) 2002-07-01 2008-09-16 Novozymes A/S Stabilization of granules
EP1517981A2 (fr) * 2002-07-01 2005-03-30 Novozymes A/S Stabilisation de granules
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EP2674475A1 (fr) * 2012-06-11 2013-12-18 The Procter & Gamble Company Composition détergente
US20170260482A1 (en) * 2016-03-08 2017-09-14 The Procter & Gamble Company Particles including enzyme
CA3067095C (fr) 2017-06-22 2023-02-14 Ecolab Usa Inc. Blanchiment a l'aide d'acide peroxyformique et d'un catalyseur a l'oxygene

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GB1590432A (en) * 1976-07-07 1981-06-03 Novo Industri As Process for the production of an enzyme granulate and the enzyme granuate thus produced
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DK161895C (da) * 1983-03-15 1992-02-03 Colgate Palmolive Co Blege- og vaskemiddel, der er fri for vandoploeselige silikater, og fremgangsmaade til blegning
GB8312185D0 (en) * 1983-05-04 1983-06-08 Unilever Plc Bleaching and cleaning composition
GB8321923D0 (en) * 1983-08-15 1983-09-14 Unilever Plc Machine-dishwashing compositions

Also Published As

Publication number Publication date
AU5932286A (en) 1987-01-08
CA1285508C (fr) 1991-07-02
EP0206418A2 (fr) 1986-12-30
EP0206418A3 (en) 1988-11-17
DE3682443D1 (de) 1991-12-19
AU585031B2 (en) 1989-06-08
JPS6279296A (ja) 1987-04-11
GR861664B (en) 1986-10-09

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