EP1517981A2 - Stabilisierung von granulat - Google Patents

Stabilisierung von granulat

Info

Publication number
EP1517981A2
EP1517981A2 EP03761448A EP03761448A EP1517981A2 EP 1517981 A2 EP1517981 A2 EP 1517981A2 EP 03761448 A EP03761448 A EP 03761448A EP 03761448 A EP03761448 A EP 03761448A EP 1517981 A2 EP1517981 A2 EP 1517981A2
Authority
EP
European Patent Office
Prior art keywords
weight
core matrix
matrix
granule
granule according
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.)
Ceased
Application number
EP03761448A
Other languages
English (en)
French (fr)
Inventor
Ole Simonsen
Erik Kjaer Markussen
Hanne Roejel
Svend Kaasgaard
Thomas Hoenger Callisen
Christian Isak Joergensen
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.)
Novozymes AS
Original Assignee
Novozymes AS
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 Novozymes AS filed Critical Novozymes AS
Publication of EP1517981A2 publication Critical patent/EP1517981A2/de
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • A—HUMAN NECESSITIES
    • A21—BAKING; EDIBLE DOUGHS
    • A21D—TREATMENT, e.g. PRESERVATION, OF FLOUR OR DOUGH, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS; PRESERVATION THEREOF
    • A21D8/00—Methods for preparing or baking dough
    • A21D8/02—Methods for preparing dough; Treating dough prior to baking
    • A21D8/04—Methods for preparing dough; Treating dough prior to baking treating dough with microorganisms or enzymes
    • A21D8/042—Methods for preparing dough; Treating dough prior to baking treating dough with microorganisms or enzymes with enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/189—Enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • A61K8/0225—Granulated powders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/63—More than one coating

Definitions

  • the present invention relates to stabilization of granules comprising an active compound e.g. an enzyme by the addition of a synthetic polymer and an antioxidant or reducing agent.
  • the invention further relates to the manufacture of said granules and the use of them.
  • US 5,972,669 discloses methods to improve the processing and storage stability of dry enzyme preparations. To this extend an inorganic salt, e.g. MgSO 4 , is dissolved in an enzyme containing solution which is subsequently dried, using e.g. spray drying.
  • WO 91/17235 discloses granules containing enzymes and an enzyme protecting agent.
  • active compounds into particles there are several reasons for formulating active compounds into particles, such as preparing enzyme granules, including protection of the active compound by separating it from the surrounding potentially hostile environment until the moment when the active compound is to be used in an application.
  • One object of the invention is to improve solid formulations for active compounds with respect to stability of the active compound.
  • polysaccharides e.g. starch to the above mentioned stabilized active compound containing matrix it further improves the stability of the granule.
  • the present invention provides in a first aspect a granule comprising a core matrix and one or more coatings, wherein the core matrix comprises: 1. an active compound; 2. a synthetic polymer, where the amount of the polymer added is 0.1 to 10 % by weight of the core matrix; 3. one or more components selected from the group of antioxidants and reducing agents, where the amount of antioxidant and reducing agent is 0.2 to 5 % by weight of the core matrix.
  • the core matrix may further comprise a polysaccharide, where the amount of polysaccharide is above 2 % by weight of the matrix.
  • the invention also provides methods for preparation of the granules and compositions comprising the granules.
  • the stability of active compounds comprised in granules is influenced by the surrounding environment upon storage, being chemical or physical factors decreasing the stability.
  • some detergent formulating agents such as bleaching agents destroy the activity of active ingredients such as enzymes.
  • Humidity is also an important factor with regard to stability of granules comprising active compounds such as enzyme granules; especially high humidity affects the stability negatively.
  • a core matrix comprising an active compound, a syn- thetic polymer and an antioxidant or reducing agent in specified amounts is found to improve the stability of the active compound significantly, improving the stability both at high and low humidity and in environments with and without hostile compounds, such as bleaching agents.
  • Synthetic polymers such as PVP are found to improve the stability of active compound containing granules, e.g. enzyme granules, especially in high humidity non hostile environment e.g. non-bleaching environments.
  • Reducing agents or antioxidants such as Sodium thiosulfate is found to improve stability of active compound containing granules, e.g. enzyme containing granules, especially in the presence of hostile compounds such as bleaching agents and in low humidity environment.
  • a further improvement we found of the granules of the invention is coating of the granules with a s alt l ayer, it i s contemplated that the salt l ayer p rolongs the l ifetime of the antioxidants or reducing agents in the core matrix even if the salt layer is very thin.
  • the granule of the present invention comprises an enzyme core matrix, one or more coatings wherein these coatings optionally may be a salt coating and a protective coating.
  • % RH is used throughout the text, and in context of the invention the term is to be understood as the relative humidity of air. 100% RH is air saturated with water moisture at a fixed temperature and % RH thus reflects the percent moisture saturation of the air.
  • high humidity is meant humidity higher than 65% RH.
  • low humidity is meant humidity below 65% RH.
  • matrix is to be understood as the mixture which comprises the active compound.
  • core matrix either makes up the entire homogenous core of the granule or makes up the mixture which is applied to a preformed inert core.
  • the core of the core is the core of the core
  • the core matrix of the invention comprises: a. an active compound; b. a synthetic polymer, where the amount of polymer added is 0.1 to 10 % by weight of the core matrix; c. one or more components selected from the group of antioxidants and reducing agents, where the amount of antioxidant and reducing agent is 0.2 to 5 % by weight of the core matrix.
  • the matrix further comprises a polysaccharide, where the amount of polysaccharide is above 2 % by weight of the matrix.
  • the active compound of the invention may be any active component or mixture of active components, which benefits from being separated from the environment surrounding the granule.
  • active is meant to encompass all compounds, which upon release from the granule upon applying the granule of the invention in a process serve a purpose of improving the p rocess. S
  • a ctive compounds a re those, which a re e ither s ubject of d eactivation and/or causing deactivation to other components in the compositions of the invention.
  • the active compound may be present dispersed as discrete solid particles in the core matrix.
  • the active compound may be inorganic of nature or organic of nature.
  • active compounds are active biological compounds which are usually very sensitive to the surrounding environment such as compounds obtainable from microorganisms. More particularly active compounds are peptides or polypeptides or proteins. Most particularly active compounds are proteins such as enzymes.
  • the enzyme in the context of the present invention may be any enzyme or combination of different enzymes. Accordingly, when reference is made to "an enzyme” this will in general be understood to include combinations of one or more enzymes.
  • enzyme variants are included within the meaning of the term "enzyme”. Examples of such enzyme variants are disclosed, e.g. in EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV).
  • enzymes which may appropriately be incorporated in granules of the invention include oxidoreductases (EC 1.-.-.-), transferases (EC 2.-.-.-), hydrolases (EC 3.-.-.-), lyases (EC 4.-.-.-), isomerases (EC 5.-.-.-) and ligases (EC 6.-.-.-).
  • Preferred oxidoreductases in the context of the invention are peroxidases (EC 1.11.1), laccases ( EC 1 .10.3.2) and g lucose oxidases ( EC 1 .1.3.4)].
  • An Example of a commercially available oxidoreductase (EC .-.-.-) is GluzymeTM (enzyme available from Novozymes A S). Further oxidoreductases are available from other suppliers.
  • Preferred transferases are transferases in any of the following sub-classes: a) Transferases transferring one-carbon groups (EC 2.1); b) transferases transferring aldehyde or ketone residues (EC 2.2); acyltransferases (EC 2.3); c) glycosyltransferases (EC 2.4); d) transferases transferring alkyl or aryl groups, other that methyl groups (EC 2.5); and e) transferases transferring nitrogeneous groups (EC 2.6).
  • transglutaminase protein-glutamine ⁇ -glutamyltransferase; EC 2.3.2.13. Further examples of suitable transglutaminases are described in WO 96/06931 (Novo
  • 3-phytases EC 3.1.3.8 and 6-phytases (EC 3.1.3.26); glycosidases (EC 3.2, which fall within a group denoted herein as " carbohydrases"), s uch a s ⁇ -amylases ( EC 3.2.1.1 ); p eptidases (EC 3.4, a Iso known a s proteases); and other carbonyl hydrolases.
  • carbohydrase is used to denote not only enzymes capable of breaking down carbohydrate chains (e.g. starches or cellulose) of especially five- and s ix-membered ring structures ( i.e. glycosidases, E C 3.2), b ut a lso enzymes capable of isomerizing carbohydrates, e.g. six-membered ring structures such as D-glucose to five- membered ring structures such as D-fructose.
  • carbohydrate chains e.g. starches or cellulose
  • five- and s ix-membered ring structures i.e. glycosidases, E C 3.2
  • b ut a lso enzymes capable of isomerizing carbohydrates e.g. six-membered ring structures such as D-glucose to five- membered ring structures such as D-fructose.
  • Carbohydrases of relevance include the following (EC numbers in parentheses): ⁇ -amylases (EC 3.2.1.1), ⁇ -amylases (EC 3.2.1.2), g lucan 1 ,4- ⁇ -glucosidases (EC 3.2.1.3), endo-1 ,4-beta-glucanase (cellulases, EC 3.2.1.4), endo-1 ,3(4)- ⁇ -glucanases (EC 3.2.1.6), endo-1 ,4- ⁇ -xylanases (EC 3.2.1.8), dextranases (EC 3.2.1.11 ), chitinases (EC 3.2.1.14), poly- galacturonases (EC 3.2.1.15), lysozymes (EC 3.2.1.17), ⁇ -glucosidases (EC 3.2.1.21), ⁇ - galactosidases (EC 3.2.1.22), ⁇ -galactosidases (EC 3.2.1.23), am
  • proteases examples include KannaseTM, EverlaseTM, EsperaseTM, AlcalaseTM, NeutraseTM, DurazymTM, SavinaseTM, PyraseTM, Pancreatic Trypsin N OVO ( PTN), B io-FeedTM Pro a nd C lear-LensTM P ro ( all available from Novozymes A/S, Bagsvaerd, Denmark).
  • proteases include MaxataseTM, MaxacalTM, MaxapemTM, OpticleanTM and PurafectTM (available from Genencor International Inc. or Gist-Brocades).
  • lipases include LipoprimeTM LipolaseTM, LipolaseTM
  • lipases include LumafastTM (Pseudomonas mendocina lipase from Genencor International Inc.); LipomaxTM (Ps. pseudoalcaligenes lipase from Gist- Brocades/Genencor Int. Inc.; and Bacillus sp. lipase from Solvay enzymes. Further lipases are available from other suppliers.
  • carbohydrases examples include Alpha-GalTM, Bio-FeedTM Alpha, Bio-FeedTM Beta, Bio-FeedTM Plus, Bio-FeedTM Plus, NovozymeTM 188, CelluclastTM, CellusoftTM, CeremylTM, CitrozymTM, DenimaxTM, DezymeTM, DextrozymeTM, FinizymTM, FungamylTM, GamanaseTM, GlucanexTM, LactozymTM, MaltogenaseTM, PentopanTM, PectinexTM, PromozymeTM, PulpzymeTM, NovamylTM, TermamylTM, AMGTM (Amyloglucosidase Novo), MaltogenaseTM, SweetzymeTM and AquazymTM (all available from Novozymes A/S). Further carbohydrases are available from other suppliers.
  • Synthetic polymers By synthetic polymers is meant polymers which backbone has been polymerised synthetically.
  • Suitable synthetic polymers of the invention includes in particular polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl a cetate, p olyacrylate, p olymethacrylate, p oly-acryla- mide, polysulfonate, polycarboxylate, and copolymers thereof, in particular water soluble poly- mers or copolymers.
  • PVP polyvinyl pyrrolidone
  • PVA polyvinyl alcohol
  • PV a cetate p olyacrylate, p olymethacrylate, p oly-acryla- mide
  • polysulfonate polycarboxylate
  • copolymers thereof in particular water soluble poly- mers or copolymers.
  • the synthetic polymer is a vinyl polymer.
  • the synthetic polymer is PVP or a copolymer thereof e.g. a PVP/vinyl acetate copolymer.
  • polyvinyl pyrrolidone we prefer to use a polymer with a molecular weight of 1 ,000 g/mol to 1 ,500,000 g/mol.
  • molecular weights below 1 ,000,000 g/mol e.g. below 800,000 g/mol, especially below 200,000 g/mol and most preferably below 100,000 g/mol.
  • the amount of synthetic polymer used in the matrix of the present invention is particularly 0.1 to 10%, more particularly 0.2 to 5 % by weight, even more particularly 0.5 to 3 % by weight, most particularly 1 to 2.5 % by weight.
  • Some synthetic polymers do have hygroscopic properties which will result in a negative effect on the stability of the granules if the amount used in the matrix is too high, and if large amounts of synthetic polymer are added the process conditions are affected in a negative way as the viscosity will become too high. If the amount of synthetic polymer is too small the stabilization effect is not seen. Furthermore synthetic polymers are expensive compared to other granulation materials so it is wishful to keep the amount necessary as low as possible. In view of these argu- ments the amount of synthetic polymer added to the matrix is a balance to reach an optimum of stabilization.
  • antioxidants and reducing agents of the present invention are salts of alkali metals and earth alkali metals, salts of sulfite, thiosulfite, thiosulfate, erythorbate, citrate, isopropyl citrate and ascorbate or corresponding acids, silicates, carbonates or bicarbonates, phosphates and nitrite, other suitable materials are methionine, glycine, propyl gallate, tert-butyl hydroquinone, tocopherols, thiodipropionic a cid, butylated h ydroxytoluene (BHT), b utylated hy- droxyanisol (BHA) or tannic acid.
  • BHT butylated h ydroxytoluene
  • BHA b utylated hy- droxyanisol
  • salts of thiosulfates e.g. sodium thiosulfate
  • the amount of antioxidant or reducing agent used in the matrix of the present invention is particularly 0.2 to 5 % by weight, more particularly 0.5 to 4 % by weight, even more particular 1 to 3 % by weight, most particular 1 to 2 % by weight of the matrix.
  • the stabilization effect may be influenced in a negative way by several things; some of the antioxidants and/or reducing agents have hygro- scopic properties which gives a negative effect in high humidity environments. Furthermore some salts do have an unpleasant odour and when used in too high amounts the smell will influence negatively on the final product. Even further when making the granules the preparation of the core matrix may include mixing the synthetic polymer and the antioxidant and/or reducing agent together with a liquid, e.g. enzyme concentrates, to get the two compounds in a dissolved form to achieve a m ore h omogenous m ixture in the core matrix. In some cases it is seen that if the amount of antioxidant or reducing agent becomes too high the synthetic polymer precipitates.
  • a liquid e.g. enzyme concentrates
  • the antioxidant or reducing agent is added to a liquid, e.g. comprising an enzyme, during preparation the solubility of the antioxidant or reducing agent can be another limiting factor.
  • the polysaccharides of the present invention may be un-modified naturally occurring polysaccharides or modified naturally occurring polysaccharides.
  • Suitable polysaccharides include cellulose, pectin, dextrin and starch.
  • the starches may be soluble or insoluble in water.
  • the polysaccharide is a starch. In a particular embodiment of the present invention the polysaccharide is an insoluble starch.
  • Naturally occurring starches from a wide variety of plant sources are suitable in the context of the invention (either as starches per se, or as the starting point for modified starches), and relevant starches include starch from: rice, corn, wheat, potato, oat, cassava, sago-palm, yuca, barley, sweet potato, sorghum, yams, rye, millet, buckwheat, arrowroot, taro, tannia, and may for example be in the form of flour.
  • Cassava starch is among preferred starches in the context of the invention; in this connection it may be mentioned that cassava and cassava starch are known under various synonyms, including tapioca, manioc, mandioca and manihot.
  • modified starch denotes a naturally occurring starch, which has undergone some kind of at least partial chemical modification, enzymatic modification, and/or physical or physicochemical modification, and which - in general - exhibits altered properties relative to the "parent" starch.
  • the amount of polysaccharides used in the matrix of the present invention is particularly above 2 % by weight, more particular 2 to 75 % by weight, even more particularly 2 to 50 % by weight, even more particularly 5 to 30 % by weight and most particularly 10 to 20 % by weight of the matrix.
  • Too high amounts of polysaccharides may result in porous granules which give a negative affect on rigidity of the granule and by that a negative effect on dust figures.
  • the amount of starch used in the matrix of the present invention is particular above 2 % by weight of the matrix, more particular above 5 % by weight.
  • the amount of starch used in the matrix of the present invention is particular 2 to 30 % by weight of the matrix, more particular above 2 to 20 % by weight, most particular 5 to 15 % by weight.
  • in-active proteins such as casein, albumin and gelatin and protein sources coming from potato, rice, corn, corn steep liquor, wheat, soy.
  • Addition of polysaccharides and/or proteins to the matrix may be in the form of enzyme fermentation broth and/or enzyme recovery sludge, but enzyme fermentation broth and/or enzyme recovery sludge may also be added besides polysaccharides and/or proteins.
  • Enzyme fer- mentation broth and enzyme recovery sludge is typically the residues from fermentation step of enzymes and following recovery step of enzymes respectively.
  • the core matrix comprises an in-active protein, which may be added in the form of enzyme fermentation broth and/or recovery sludge.
  • the core matrix comprises: a. an active compound; b. a synthetic polymer, where the amount of polymer added is 0.1 to 10 % by weight of the matrix; c. one or more antioxidants and/or reducing agents, where the amount of antioxidant and/or reducing agent is 0.2 to 5 % by weight of the matrix; d. a polysaccharide, where the amount of polysaccharide is above 2 % by weight of the matrix.
  • the synthetic polymer is PVP
  • the antioxidant is sodium thiosulfate
  • the polysaccharide is starch.
  • the matrix may further comprise a soluble inorganic salt, wherein said inorganic salt com- prises a divalent cation selected from the group of zinc, magnesium and calcium, in particular Magnesium sulfate and zinc sulfate. Divalent cations are preferred because they provide the best storage and processing stability. Sulfate is preferred as anion because it provides the best drying yield.
  • the salt is magnesium sulfate. Salts mentioned in the section "Coatings" (below) may also be used.
  • the amount of salt used in the matrix of the present invention is particularly 1 to 70 % by weight, more particularly 2 to 30 % by weight more particularly 2 to 10 % by weight.
  • the matrix may further comprise known conventional core material as auxiliary matrix components such as binders, solvents, fillers etc. these are described in WO 89/08694, WO 89/08695, EP 270608 B1 and/or WO 00/01793.
  • the core matrix may optionally be coated onto a preformed core.
  • Preformed cores also called carrier nuclei, placebo nuclei (nucleus free of active compound) or seeds are inert particles upon which the mixture comprising the active compound can be layered.
  • the preformed cores may comprise inorganic salts, sugars, sugar alcohols, small organic molecules such as organic acids or salts, minerals such as clays or silicates or a combination of two or more of these.
  • the core may be prepared by applying the mixture comprising the active compound onto a preformed core.
  • the granule m ay comprise o ne o r more coatings.
  • the coatings may b e from 1 ⁇ to 1500 ⁇ thick.
  • the coating is more than 30 ⁇ thick, in a more particular embodiment the coating is more than 50 ⁇ thick, in a most particular embodiment the coat- ing is more than 75 ⁇ thick.
  • the coating is less than 1000 ⁇ thick, in a more particular embodiment the coating is less than 500 ⁇ thick, in an even more particular embodiment the coating is less than 250 ⁇ thick, in a most particular embodiment the coating is less than 150 ⁇ thick.
  • the granules comprise a thin salt coating.
  • a salt coating which is 2 to 5 ⁇ thick shows a significant improvement in stability.
  • the salt coating comprise 2 to 30 % by weight of the matrix and the salt coating.
  • the amount of salt is 3 to 10 % by weight of the matrix and the salt coating.
  • the salt coating may for other reasons than stability be a thick coating such as protection and integrity.
  • the thickness of the salt coating is 1 ⁇ to 1000 ⁇ thick. In a more particular embodiment of the present invention the salt coating is 2 ⁇ to 100 ⁇ thick. In an even more particular embodiment of the present invention the salt coating is 3 ⁇ to 20 ⁇ thick.
  • the salt coating is less than 500 ⁇ thick. In a more particular embodiment the salt coating is less than 250 ⁇ thick. In an even more particular embodiment of
  • the salt coating is less than 100 ⁇ thick. In an even more particular embodiment of the present invention the salt coating is less than 80 ⁇ thick. In a more particular embodiment of the present invention the salt coating is less than 50 ⁇ thick. In a most particular embodiment the salt coating is less than 30 ⁇ thick. 1
  • the salt coating comprises one or more salts.
  • the salt may be an inorganic salt, e.g.
  • simple organic acids less than 10 carbon atoms e.g. 6 or less carbon atoms
  • Examples of cations in these salt are alkali or earth alkali metal ions, although the ammonium ion or metal ions of the first transition series, such as sodium, potas-
  • anions include chloride, bromide, 5 iodide, sulfate, sulfite, bisulfite, thiosulfate, phosphate, m onobasic phosphate, dibasic phosphate, hypophosphite, dihydrogen pyrophosphate, tetraborate, borate, carbonate, bicarbonate, metasilicate, citrate, malate, maleate, malonate, succinate, lactate, formate, acetate, butyrate, propionate, benzoate, tartrate, ascorbate or gluconate.
  • salts of sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate or salts of sim- '0 pie organic acids such as citrate, malonate or acetate may be used.
  • Specific examples include
  • the salt may also be a hydrated salt, i.e. a crystalline salt hydrate with bound water(s)
  • the granule comprising the matrix and optionally a salt coating may further be coated with one or more coating layers to provide further improved properties of the granule.
  • Conventional coatings and methods as known to the art may suitably be used, such as the coatings described in WO 89/08694, WO 89/08695, 270 608 B1 and/or WO 00/01793.
  • Other examples of conventional coating materials may be found in US 4,106,991, EP 170360, EP 304332, EP
  • the coating may comprise materials selected from binders, fibers, salts, water insoluble minerals, pigments, dyes, enzyme stabilizers or combinations thereof and any granulation 5 materials mentioned above in the section "The core".
  • hostile compounds are compounds which are found to decrease the activity of the active compound.
  • hostile compounds can be but are not limited to bleaching agents, alkaline components, anionic surfactants, metal complexing agents (e.g. 10 builders).
  • the invention further encompasses a process for preparing a g ranule, comprising the steps of: a. preparing a core matrix comprising an active compound; a synthetic polymer in an 15 amount of 0.1 to 10 % by weight of the core matrix; and a component selected from the group consisting of antioxidants and reducing agents in an amount of 0.2 to 5 % by weight of the core matrix; b. and applying one or more coatings to said core matrix.
  • the granules may be prepared by methods known to those skilled in the art of enzyme granulation, including mixer granulation, fluid bed coating, prilling, disc granulation, pan drum coating, spray drying, extrusion, fluid bed spray drying, high shear agglomeration, spheronization or combinations of these techniques.
  • Methods for preparing the core matrix particles include known enzyme granule formulation technologies e.g. spray drying, fluid bed, fluid bed spray drying, mixer granulation, pan drum process and extrusion.
  • Other relevant core particles are layered products, absorbed products, pelletized products, prilled products.
  • the cores may optionally be dried after granulation.
  • Spray dried products may be prepared by a liquid enzyme-containing solution which is atomised in a spray drying tower to form small droplets which during their way down the drying tower dry to form an enzyme-containing particulate material. Very small particles can be produced this way (Michael S. Showell (editor); Powdered detergents; Surfactant Science Series; 1998; vol. 71 ; page 140-142; Marcel Dekker).
  • Layered products includes products where enzyme is coated as a layer around a preformed inert core particle, wherein an enzyme-containing solution is atomised, typically in a fluid bed apparatus wherein the pre-formed core particles are fluidised, and the enzyme-containing solution adheres to the core particles and dries up to leave a layer of dry enzyme on the surface of the core particle. Particles of a desired size can be obtained this way if a useful core particle of the desired size can be found. This type of product is described in e.g. WO 97/23606.
  • the enzyme is absorbed onto and/or into the surface of the core, rather than coating the enzyme as a layer around the core. Such a process is described in WO 97/39116.
  • Extrusion or pelletized products may be prepared by an enzyme-containing paste is pressed to pellets or under pressure is extruded through a small opening and cut into particles which are subsequently dried. Such particles usually have a considerable size because of the ma- terial in which the extrusion opening is made (usually a plate with bore holes) sets a limit on the allowable pressure drop over the extrusion opening. Also, very high extrusion pressures when using a small opening increase heat generation in the enzyme paste, which is harmful to the enzyme. (Michael S. Showell (editor); Powdered detergents; Surfactant Science Series; 1998; vol. 71 ; page 140-142; Marcel Dekker).
  • the syn- thetic polymer and/or the polysaccharide and/or the protein source and/or the antioxidants are mixed together with a liquid e.g. enzyme concentrate or fermentation broth and then extruded.
  • Prilled products includes products where an enzyme powder is suspended in molten wax and the s uspension is s prayed, e .g. through a rotating d isk atomiser, i nto a cooling chamber where the droplets quickly solidify (Michael S. Showell (editor); Powdered detergents; Surfactant Science Series; 1998; vol. 71; page 140-142; Marcel Dekker).
  • the product obtained is one wherein the enzyme is uniformly distributed throughout an inert material instead of being concentrated on its surface.
  • US 4,016,040 and US 4,713,245 are documents relating to this technique .
  • Mixer granulation products includes products where an enzyme-containing liquid is added to a dry powder composition of conventional granulating components.
  • the liquid and the powder in a suitable proportion are mixed and as the moisture of the liquid is absorbed in the dry powder, the components of the dry powder will start to adhere and agglomerate and particles will build up, forming granulates comprising the enzyme.
  • Such a process is described in US 4,106,991 (NOVO NORDISK) and related documents EP 170360 B1 (NOVO NORDISK), EP 304332 B1 (NOVO NORDISK), EP 304331 (NOVO NORDISK), WO 90/09440 (NOVO NORDISK) and WO 90/09428 (NOVO NORDISK).
  • Methods for preparing a visco-elastic liquid core particle include those described in WO 02/28991 and is hereby incorporated by reference.
  • the synthetic polymer and/or the polysaccharide and/or the protein source and or the antioxidants are mixed together with a liquid e.g. enzyme concentrate or fermentation broth and then atomised onto preformed cores in a coating chamber e.g. a fluid bed, a multistage fluid bed, a fluid bed spray drier optionally with recirculation of fine particles.
  • the salt coating may be applied onto the granule comprising the matrix comprising the active compound by atomization onto the granules in a fluid bed or a fluid bed spray dryer, the salt- coating may further be applied i n vacuum m ixers, d ragee type coaters ( pan-drum coaters), equipment for coating of seeds, equipment comprising rotating bottoms (eks. Roto Glatt, CF granulators (Freund), torbed processors (Gauda) or in rotating fluid bed processors such as Omnitex (Nara).
  • the granule may optionally be dried.
  • the drying of the salt coated granule can be achieved by any drying method available to the skilled person, such as spray- drying, freeze drying, vacuum drying, fluid bed drying, pan drum coating and microwave dry- ing. Drying of the salt coated granule can also be combined with granulation methods which comprise e.g. the use of a fluid bed, a fluid bed spray dryer (FSD) or a Multi-stage dryer (MSD).
  • FSD fluid bed spray dryer
  • MSD Multi-stage dryer
  • the coating may be prepared by the same methods as mentioned above in the section "Preparation of the core matrix” and “Preparation of the salt coating”. Compositions comprising the coated particle and their application
  • the invention also relates to compositions comprising the granules of the invention.
  • the composition may be any composition, but particularly the compositions which are well suited are cleaning compositions, textile processing compositions, leather processing compositions, pulp or paper processing compositions, food and beverage compositions, animal feed compositions, pharmaceutical compositions and personal care compositions.
  • Cleaning compositions includes detergents and anti-microbial compositions.
  • Textile processing compositions includes compositions for enzymatic bleach and/or stone washing of textiles, s uch as d enim.
  • F ood a nd beverage compositions i n cludes e nzymatic compositions used in industries producing wine, oils and fats, citrus and juice products, starch and sugar products, alcohols and/or brewed products, soy products and baking flour or dough.
  • the present invention also encompasses the use for treatment of textile, leather, pulp, paper, food, beverage, hard surfaces and the human or animal body.
  • the granules may also be used in the manufacture of a medicament for treatment of the human or animal body.
  • coated particles of the invention may be added to and thus become a component of a detergent composition.
  • the detergent composition of the invention may for example be formulated as laundry de- tergent composition for hand or machine washings including a cleaning additive composition suitable for pre-treatment of stained fabrics or a fabric softener composition, or a detergent composition for use in general household hard surface cleaning operations, or a composition for hand or machine dishwashing operations.
  • the invention provides a detergent additive comprising the coated par- tides of the invention.
  • the detergent additive as well as the detergent composition may comprise one or more other enzymes such as a protease, a lipase, a cutinase, an amylase, a carbohy- drase, a cellulase, a pectinase, a mannanase, an arabinase, a galactanase, a xylanase, an oxi- dase, e.g., a laccase, and/or a peroxidase.
  • enzymes such as a protease, a lipase, a cutinase, an amylase, a carbohy- drase, a cellulase, a pectinase, a mannanase, an arabinase, a galactanase, a xylana
  • the properties of the chosen enzyme(s) should be compatible with the selected detergent, (i.e. pH-optimum, compatibility with other enzymatic and non-enzymatic ingredients, etc.), and the enzyme(s) should be present in effective amounts.
  • proteases include those of animal, vegetable or microbial origin. Mi- crobial origin is preferred. Chemically modified or protein engineered mutants are included.
  • the protease may be a serine protease or a metallo protease, preferably an alkaline microbial prote- ase or a trypsin-like protease.
  • alkaline proteases are subtilisins, especially those derived from Bacillus, e.g., subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and sub- tilisin 168 (described in WO 89/06279).
  • trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270 and WO 94/25583.
  • Examples of useful proteases are the variants described in WO 92/19729, WO 98/20115, WO 98/20116, and WO 98/34946, especially the variants with substitutions in one or more of the following positions: 27, 36, 57, 76, 87, 97, 101, 104, 120, 123, 167, 170, 194, 206, 218, 222, 224, 235 and 274.
  • Preferred commercially available protease enzymes include EVERLASETM, OVOZYMETM, SAVOZYMETM, ALCALASETM, SAVINASETM, PRIMASETM, DURALASETM, ESPERASETM, AND KANNASETM (Novozymes A/S), MAXATASETM, MAXACALTM, MAXAPEMTM, PROPERASETM, PURAFECTTM, PURAFECT OXPTM, FN2TM, and FN3TM, FN4TM (Genencor International Inc.).
  • Lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humi- cola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P.
  • Preferred commercially available lipase enzymes include LIPOLASETM and LIPOLASE ULTRATM (Novozymes A/S).
  • Amylases Suitable amylases ( ⁇ and/or ⁇ ) include those of bacterial or fungal origin.
  • Amylases include, for example, ⁇ -amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1 ,296,839.
  • Examples of useful amylases are the variants described in WO 94/02597, WO 94/18314, WO 96/23873, and WO 97/43424, especially the variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181 , 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g.
  • cellulases are the alkaline or neutral cellulases having colour care benefits.
  • Examples of such cellulases are cellulases described in EP 0 495 257, EP 0 531 372,
  • WO 96/11262 WO 96/29397, WO 98/08940.
  • Other examples are cellulase variants such as those described in WO 94/07998, EP 0 531 315, US 5,457,046, US 5,686,593, US 5,763,254, WO 95/24471 , WO 98/12307 and PCT/DK98/00299.
  • cellulases include CELLUZYMETM, and CAREZYMETM (Novozymes A/S), CLAZINASETM, and PURADAX HATM (Genencor International Inc.), and KAC- 500(B) TM (Kao Corporation).
  • Peroxidases/Oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257.
  • peroxidases include GUARDZYMETM (Novozymes A/S).
  • Suitable mannanases include MANNAWAYTM(Novozymes A/S).
  • the detergent enzyme(s) may be included in a detergent composition by adding separate additives containing one or more enzymes, or by adding a combined additive comprising all of these enzymes.
  • a detergent additive of the invention i.e. a separate additive or a combined additive, may be formulated so as to contain one or more of the particles of the invention comprising different enzymes.
  • the detergent composition of the invention may be in any convenient dry form, e.g., a bar, a tablet, a powder, a granule or a paste. It may also be a liquid detergent, in particular non- aqueous liquid detergent.
  • the detergent composition comprises one or more surfactants, which may be non-ionic including semi-polar and/or anionic and/or cationic and/or zwitterionic.
  • the surfactants are typi- cally present at a level of from 0.1 % to 60% by weight.
  • the detergent When included therein the detergent will usually contain from about 1 % to about 40% of an anionic surfactant such as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
  • an anionic surfactant such as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
  • the detergent When included therein the detergent will usually contain from about 0.2% to about 40% of a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, al- kyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides").
  • a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, al- kyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
  • glucamides N-acyl N-alkyl derivatives of glucosamine
  • the detergent may contain 0-65 % of a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, carbonate, citrate, nitrilotriacetic acid, ethyl- enediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst).
  • a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, carbonate, citrate, nitrilotriacetic acid, ethyl- enediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst).
  • the detergent may comprise one or more polymers.
  • Examples are carboxymethylcellu- lose, poly(vinylpyrrolidone), poly (ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • the detergent may contain a bleaching system, which may comprise a H2O2 source such as perborate or percarbonate, which may be combined with a peracid-forming bleach activator such as tetraacetylethylenediamine or nonanoyloxybenzenesulfonate.
  • a bleaching system may comprise peroxyacids of e.g. the amide, imide, or sulfone type.
  • the enzyme(s) of the detergent composition of the invention may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric a cid derivative, e .g., a n aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
  • the detergent may also contain other conventional detergent ingredients such as e.g.
  • fabric conditioners including clays, foam boosters, suds suppressors, anti-corrosion agents, soil- suspending agents, anti-soil redeposition agents, dyes, bactericides, optical brighteners, hydro- tropes, tarnish inhibitors, or perfumes.
  • any enzyme may be added in an amount corresponding to 0.01-100 mg of enzyme protein per litre of wash liquor, preferably 0.05-5 mg of enzyme protein per litre of wash liquor, in particular 0.1-1 mg of enzyme protein per litre of wash liquor.
  • the enzyme of the invention may additionally be incorporated in the detergent formulations disclosed in WO 97/07202, which is hereby incorporated as reference.
  • Uncoated protease granulates were produced by: A powder composition prepared from the following (all percentages given as % of dry granu- late): 10% Fibrous cellulose (Arbocel BC 200)
  • Finely ground sodium sulfate ad 100% was mixed in a Lodige mixer and sprayed with protease (SAVINASETM) ultrafiltrate wherein 5% sugar and stabilizers as given in the examples were dissolved.
  • the moist mixture was exposed to a compacting and granulating influence as described in example 1 of US patent No. 4,106,991.
  • the granulate was subsequently dried in a fluid bed.
  • the stability of the enzyme granulates in different powder detergents and at different conditions was measured by adding 2% of the produced granulates to the detergent and storing the samples in climate chambers in open beakers.
  • Stability design I: 4 weeks at 35°C/55% RH (low humidity) bleach containing powder detergent II: 2 weeks at 37°C/70% RH (high humidity) bleach containing powder detergent III: 4 weeks at 37°C/70% RH (high humidity) non-bleach powder detergent:
  • This example illustrates how PVP increases the stability in high humidity environments.
  • Granules were prepared as in example 1.
  • This example illustrates how sodium thiosulfate increases the stability in low humidity and in bleach containing environments.
  • Granules were prepared as in example 1.
  • This example illustrates how a polysaccharide such as rice starch increases the stability in high and low humidity environments and in bleach containing and none bleach environments.
  • Granules were prepared as described in example 1 and subsequently coated in a fluid bed with 5% sodium sulfate (by spraying an aqueous liquid composed by 28% sodium sulfate, 1% dextrin and 4% titan dioxide onto the granulates). The granulates were further coated with wax as given in WO 97/39116 example 18. Finally the granules were fluid bed coated with 3% Sepifilm (by spraying an aqueous solution of 15% Sepifilm LP030 from Seppic onto the granulates).
  • Granules were prepared as described in example 1, but also using finely ground MgSO 4 -7H 2 O as filler instead of sodium sulfate, and subsequently coated in a fluid bed with 5% sodium sulfate (by spraying an aqueous liquid composed by 28% sodium sulfate, 1% dextrin and 4% titan dioxide onto the granulates).
  • the granulates were further coated with wax as given in WO 97/39116 example 18.
  • Finally the granules were fluid bed coated with 3% Sepifilm (by spraying an aqueous solution of 15% Sepifilm LP030 from Seppic onto the granulates).
  • Example 6 Granules were prepared as given in example 1 , but also using Luviskol VA64 (A 60/40 copolymer of vinyl-pyrrolidon and vinyl acetate from BASF) as synthetic polymer.
  • Luviskol VA64 A 60/40 copolymer of vinyl-pyrrolidon and vinyl acetate from BASF
  • Granules were prepared as given in example 4 (i.e. with a 5% salt coating), but without the final Sepifilm and using both rice and corn starch.
  • Granules were prepared as given in example 7 (i.e. with a 5% salt coating but no Sepifilm), using different enzyme types.
  • This example illustrates that the stabilization system is efficient on different enzyme types.

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CN112533486A (zh) * 2018-03-16 2021-03-19 味之素株式会社 饲料用添加剂及饲料
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CN108998276B (zh) * 2018-08-03 2021-05-14 东莞市激浪洗涤科技有限公司 一种含有还原增白剂的洗衣粉及其制备方法
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