CN1656205A - Stabilization of granules - Google Patents

Stabilization of granules Download PDF

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Publication number
CN1656205A
CN1656205A CNA038124726A CN03812472A CN1656205A CN 1656205 A CN1656205 A CN 1656205A CN A038124726 A CNA038124726 A CN A038124726A CN 03812472 A CN03812472 A CN 03812472A CN 1656205 A CN1656205 A CN 1656205A
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China
Prior art keywords
particle
core matrix
weight
enzyme
composition
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CNA038124726A
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Chinese (zh)
Inventor
O·西蒙森
E·K·马库森
H·罗杰
S·卡斯伽德
T·H·卡利森
C·I·约恩森
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Novozymes AS
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Novozymes AS
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Publication of CN1656205A publication Critical patent/CN1656205A/en
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    • 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

Abstract

The present invention relates to granules comprising a core matrix and one or more coatings, wherein the core matrix comprises: An active compound, a synthetic polymer, where the amount of polymer added is 0.1 to 10 % by weight of the matrix, and 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. The active compound is an enzyme, e.g. savinase. The synthetic polymer is a polyvinyl polymer selected from the group consisting of PVP, PVA and copolymers thereof. A preferred antioxidant is sodium thiosulfate.

Description

Particulate is stable
The present invention relates to by adding the stable for example particle of enzyme of active compound that contains of synthetic polymkeric substance and antioxidant or reductive agent.The invention still further relates to described particulate produces and uses thereof.
Background of invention
Active compound is incorporated in drying solid particle or the particle and prevents the active substance inactivation thus and/or prevent that external environment from contacting with active substance is known in the art.It also is known in the art to protect compound to avoid the inactivation that the aggressiveness material causes in the environment that stablizer is mixed the particle that contains activeconstituents.
Relate to and stablize that the known existing document of active compound comprises US 5,858,952 in the dried particles, its disclose contain enzyme and one or more be selected from reductive agent and antioxidant stablizer contain the enzyme granulated product.
US 5,972, and 669 disclose the processing that improves dry zymin and the method for storage stability.For this reason, with inorganic salt MgSO for example 4Be dissolved in and contain enzyme solution, it is used for example spray-drying process drying subsequently.
WO 91/17235 discloses the particle that contains enzyme and enzymatic protective reagent.
Summary of the invention
Have several reasons active compound need be prepared in the particle, as the preparation enzyme granulate, these reasons be included in active compound face with before that time with active substance and on every side potential adverse environment separate.
For enzyme containing granule, disadvantageous bleaching component can produce stable problem in the stain remover especially.High humidity in the surrounding environment is enzyme containing granule to be caused another parameter of stability problem.
Obtain containing active compound such as enzyme and high humidity, low humidity and with particle all stable with not with unfavorable composition combination the time be very difficult.
We in the research that improves enzyme granulate, be surprisingly found out that the synthetic polymkeric substance for example PVP and antioxidant or reductive agent for example the combination of Sulfothiorine the stable of in all adverse environments above-mentioned active compound is provided, cause when they mix in matrix with specified quantitative that the stability of active compound significantly improves in the particle.
An object of the present invention is aspect active compound stable, to improve the solid preparation of these active compounds.In our research to the preparation of these improvement, we also have been found that by with polysaccharide for example starch join the matrix that contains the active compound that is stabilized above-mentioned, can further improve particulate stability.
Thereby one aspect of the present invention provides and has contained core matrix and one or more layers coated granules, and wherein core matrix contains:
1. active compound;
2. synthetic polymer, wherein the amount of polymers of Jia Ruing is 0.1 to 10% of core matrix by weight;
3. one or more are selected from the component of antioxidant and reductive agent, and wherein the amount of antioxidant and reductive agent is 0.2 to 5% of core matrix by weight.
Core matrix can also contain polysaccharide, and wherein the amount of polysaccharide is higher than 2% of matrix by weight.
The present invention also provides the method for preparing particle and contain grains of composition.
Detailed Description Of The Invention
The stability of contained active compound is subjected to the influence of surrounding environment in the particle when preserving, and chemistry or physical factor reduce its stability.In the stain remover preparation, the reagent of some preparation stain removers such as SYNTHETIC OPTICAL WHITNER are destroyed the activity of activeconstituents such as enzyme.
Humidity also is an important factor about the stability of particle that contains active compound such as enzyme granulate; Especially, high humidity negative impact stability.
So far, also do not report such particle that contains active compound, wherein active compound is at high humidity and low humidity and comprising and do not comprising in the environment of unfavorable compound such as SYNTHETIC OPTICAL WHITNER and all stablize.
We it has surprisingly been found that the core matrix of the active compound, synthetic polymer and the antioxidant that contain specified quantitative or reductive agent significantly improves the stability of active compound, at high humidity and low humidity and have and do not have and all improve stability in the environment of unfavorable compound such as SYNTHETIC OPTICAL WHITNER.
Find that synthetic polymer such as PVP improve the particle stability of enzyme granulate for example that contains active compound, particularly in high humidity and for example non-bleaching environment of no unfavorable environment.Find that reductive agent or antioxidant such as Sulfothiorine improve the particle stability of enzyme containing granule for example that contains active compound, when particularly having unfavorable compound such as SYNTHETIC OPTICAL WHITNER and low-humidity environment.
Therefore, by in matrix, active compound and synthetic polymer such as PVP and reductive agent or antioxidant such as Sulfothiorine being mixed, can prepare wherein even at some extremely in the hostile environment active compound that the stability of active compound also significantly improves.By this combination of particulate component, the scope that can stablize the active compound in the particle of the present invention under varying environment has obviously enlarged.
That we find that also polysaccharide improves is unfavorable/all of non-unfavorable and low humidity/high humidity environment make up in the stability of active compound.
Also find to pass through with MgSO 4Add in the core matrix above-mentioned, it further improves the stability of active compound.
We find that it is to use the salt deposit coated granule that particulate of the present invention further improves, even think that salt deposit is extremely thin, it also prolongs the life-span of antioxidant in the core matrix or reductive agent.
Particle of the present invention contains the enzyme core matrix, one or more layers dressing, and wherein these dressings randomly can be salt dressing or protectiveness dressing.
Definition
Term " %RH " uses in the text, and this term will be understood that the relative humidity of air in the context of the present invention.100%RH be under the fixed temperature by the air of water saturation, thereby %RH has reacted the water saturation percentage ratio of air.
High humidity refers to that humidity is higher than 65%.
Low humidity refers to that humidity is lower than 65%.
Term " matrix " is interpreted as the mixture that contains active compound." core matrix " or all even cores of formation particulate or formation are applied to the mixture of preformed inertia core.
Core
Core matrix of the present invention contains:
A. active compound;
B. synthetic polymer, wherein the amount of the polymkeric substance of Jia Ruing is 0.1 to 10% of core matrix by weight;
C. be selected from one or more components of antioxidant and reductive agent, wherein the amount of antioxidant and reductive agent is 0.2 to 5% of core matrix by weight.
In a specific embodiment of the present invention, matrix also contains polysaccharide, and wherein the amount of polysaccharide is more than 2% of matrix by weight.
Active compound
Active compound of the present invention can be the mixture of any active ingredient or active ingredient, and it has benefited from from separating around the particulate environment.Term " active " is intended to comprise all compounds, and these compounds discharge from particle and play the purpose of improving this process when using particle of the present invention in certain process.Suitable active compound for those by other component inactivations in the composition of the present invention and/or make the compound of those component inactivations.Active compound can be used as the dispersion solid particle that is scattered in the core matrix and exists.
Active compound can be inorganic or organic.Particularly, active compound is usually to the highstrung bioactive compounds of surrounding environment, as the compound that obtains from microorganism.More specifically, active compound is peptide or polypeptide or protein.The most particularly, active compound is protein such as enzyme.
Enzyme in the context of the invention can be the combination of any enzyme or different enzymes.Therefore, this is understood to include the combination of one or more enzymes usually when referring to " enzyme ".
Should be appreciated that term " enzyme " comprises enzyme variants (for example producing by recombinant technology).The example of these enzyme variants is for example disclosing among EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and the WO 94/02618 (Gist-Brocades NV).
The foundation that is applied to the enzyme classification in this specification and claims book is the suggestion (1992) of international biological chemistry and NK of molecular biology association, Academic Press, Inc., 1992 (Recommendation (1992) of the Nomenclture committee of theInternational Union of Biochemistry and Molecular Biology).
Therefore, the type that is suitable for being combined in the enzyme in the particle of the present invention comprises oxydo-reductase (EC1.-.-.-), transferring enzyme (EC 2.-.-.-), lytic enzyme (EC 3.-.-.-), lyase (EC 4.-.-.-), isomerase (EC 5.-.-.-) and ligase enzyme (EC 6.-.-.-).
In the context of the invention, preferred oxydo-reductase is peroxidase (EC.1.11.1), laccase (EC 1.10.3.2) and glucose oxidase (EC 1.1.3.4)].The example of commercialization oxydo-reductase (EC 1.-.-.-) has Gluzyme TM(from the enzyme of Novozymes A/S).Other oxydo-reductase can obtain from other dealer.Preferred transferring enzyme is the transferring enzyme that belongs to following any subclass:
A) transferring enzyme (EC 2.1) of the single carbon-based group of transfer;
B) transferring enzyme (EC 2.2) of transfer aldehydes or ketones residue; Acyltransferase (EC 2.3);
C) glycosyltransferase (EC 2.4);
D) transferring enzyme (EC 2.5) of the alkyl or aryl group of transfer except that methyl group; And
E) transferring enzyme (EC 2.6) of transfer nitrogen-containing group.
A most preferred type that can be used for the transferring enzyme among the present invention is a trans-glutaminases (protein-glutamine gamma glutamyltransferase; EC 2.3.2.13).
Other example of suitable trans-glutaminases is referring to the explanation of WO 96/06931 (Novo NordiskA/S).
Lytic enzyme especially can be in the context of the invention: carboxylic ester hydrolase (EC 3.1.1.-) is as lipase (EC 3.1.1.3); Phytase (EC 3.1.3.-) is as 3-phytase (EC 3.1.3.8) and 6-phytase (EC 3.1.3.26); Glycosylase (EC 3.2, and it belongs to alleged " carbohydrase " herein) is as α-Dian Fenmei (EC 3.2.1.1); Peptase (EC 3.4, are also referred to as proteolytic enzyme); And other carbonylic hydrolase.
In the present invention, term " carbohydrase " not only be used in reference to and can rupture and have especially the sugar chain of 5 and 6 ring structures (as, starch or Mierocrystalline cellulose) enzyme (be Glycosylase, EC 3.2), but also refer to make the isomerized enzyme of carbohydrate, for example 6 ring structures such as D-glucose isomerase are turned to 5 ring structures such as D-fructose.
Suitable carbohydrase comprises following (being the EC numbering in the bracket): α-Dian Fenmei (EC3.2.1.1), beta-amylase (EC 3.2.1.2), dextran 1,4-alpha-glucosidase (EC 3.2.1.3), inscribe-1,4-beta-glucanase (cellulase, EC 3.2.1.4), inscribe-1,3 (4)-beta-glucanases (EC3.2.1.6), inscribe-1,4-beta-xylanase (EC 3.2.1.8), dextranase (EC 3.2.1.11), chitinase (EC 3.2.1.14), polygalacturonase (EC 3.2.1.15), N,O-Diacetylmuramidase (EC 3.2.1.17), beta-glucosidase enzyme (EC 3.2.1.21), alpha-galactosidase (EC 3.2.1.22), beta-galactosidase enzymes (EC3.2.1.23), amylo-1:4,1:6-transglucosidase, 6-Polyglucosidase (EC 3.2.1.33), xylan 1,4-xylobiase (EC3.2.1.37), dextran inscribe-1,3-β-D-Polyglucosidase (EC 3.2.1.39), Schardinger dextrin inscribe-1,6-alpha-glucosidase (EC3.2.1.41), sucrose alpha-glucosidase (EC 3.2.1.48), dextran inscribe-1,3-alpha-glucosidase (EC 3.2.1.59), dextran 1,4-beta-glucosidase enzyme (EC 3.2.1.74), dextran inscribe-1,6-beta-glucosidase enzyme (EC 3.2.1.75), arabinan inscribe-1,5-α-L-arabinose glycosides enzyme (EC 3.2.1.99), Sumylact L (EC 3.2.1.108), chitosanase (EC 3.2.1.132) and xylose isomerase (EC 5.3.1.5).
The example of commercial proteolytic enzyme (peptase) comprises Kannase TM, Everlase TM, Esperase TMAlcalase TM, Neutrase TM, Durazym TM, Savinase TM, Pyrase TM, Pancreatic Trypsin Novo (PTN), Bio-Feed TMPro and Clear-Lens TMPro (all from Novo zymes A/S, Bagsvaerd, Denmark).
Other commercial proteolytic enzyme comprises Maxatase TM, Maxacal TM, Maxapem TM, Opticlean TMAnd Purafect TM(from Genencor International Inc. or Gist-Brocades).
The example of commercial lipase comprises Lipoprime TM, Lipolase TM, Lipolase TMUltra, Lipozyme TM, Palatase TM, Novozym TM435 and Lecitase TM(all from Novozymes A/S).
Other commercial lipase comprises Lumafast TM(pseudomonas mendocina of Genencor International Inc. (Pseudomonas mendocina) lipase); Lipomax TM(the pseudomonas pseudoalcaligenes of GistBrocades/Genencor Int.Inc (Ps.pseudoalcligenes) lipase; And the bacillus of Solvay Enzymes (Bacillus) lipase.Other lipase can obtain from other dealer.
The example of commercial carbohydrase comprises Alpha-Gal TM, Bio-Feed TMAlpha, Bio-Feed TMBeta, Bio-Feed TMPlus, Bio-Feed TMPlus, Novozyme TM188, Celluclast TM, Cellusoft TM, Ceremyl TM, Citrozym TM, Denimax TM, Dezyme TM, Dextrozyme TM, Finizym TM, Fungamyl TM, Gamanase TM, Glucanex TM, Lactozym TM, Maltogenase TM, Pentopan TM, Pectinex TM, Promozyme TM, Pulpzyme TM, Novamyl TM, Termamyl TM, Amg TM(amyloglucosidase Novo), Maltogenase TM, Sweetzyme TMAnd Aquazym TM(all from Novozymes A/S).Other carbohydrase can be from other dealer.
Synthetic polymer
Synthetic polymer is meant its main chain polymeric polymkeric substance by synthesizing.
Suitable synthetic polymer of the present invention is particularly including polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate, polyacrylic ester, polymethacrylate, polyacrylamide, polysulfonates, polycarboxylate, and multipolymer, especially water miscible polymkeric substance or multipolymer.
In a particular of the present invention, synthetic polymer is an ethene polymers.
In a preferred embodiment of the invention, synthetic polymer is PVP or its multipolymer, for example PVP/ vinyl acetate copolymer.
When using polyvinylpyrrolidone, we preferably use molecular weight is 1,000g/mol to 1,500, the polymkeric substance of 000g/mol.For satisfactory stability, we are lower than 1,000 at preferred molecular weight, and 000g/mol for example is lower than 800, and 000g/mol particularly is lower than 200, and 000g/mol most preferably is lower than 100,000g/mol.We are higher than 5 at preferred usually the use, and 000g/mol particularly is higher than 10, and 000g/mol the most especially is higher than 20, and 000g/mol for example is higher than 25, the molecular weight of 000g/mol.
The amount of the synthetic polymer that in matrix of the present invention, uses by weight especially 0.1 to 10%, more particularly 0.2 to 5%, even more particularly 0.5 to 3%, the most especially 1 to 2.5%.
Some synthetic polymers have hygroscopic nature, and the amount of using in matrix when them will have a negative impact to particulate stability when too big, if a large amount of synthetic polymer is added into, processing conditions will be subjected to negative impact so, because viscosity will be very high.If the amount of synthetic polymer is too little, so just cannot see stabilising effect.In addition, compare with other granulated materials, synthetic polymer is more expensive, therefore wishes to keep its consumption low as far as possible.Consider these arguments, the amount that adds the synthetic polymer of matrix is the balance that reaches best stabilized.
Antioxidant and reductive agent
The example of suitable antioxidant of the present invention and reductive agent is basic metal and alkaline earth salt, sulphite, thiosulfite, thiosulphate, erythorbate, Citrate trianion, sec.-propyl Citrate trianion and ascorbate salt or corresponding acid, silicate, carbonate, supercarbonate, phosphoric acid salt and nitrite, and other suitable materials are methionine(Met), glycine, propyl gallate, tertiary butylated hydroquinone, tocopherol, thio-2 acid, butylated hydroxytoluene (BHT), fourth hydroxyanisol (BHA) or Weibull.Thiosulphate, for example Sulfothiorine is especially suitable.The antioxidant that uses in the matrix of the present invention or the amount of reductive agent be by matrix weight especially 0.2 to 5%, and more particularly 0.5 to 4%, even more particularly 1 to 3%, the most especially 1 to 2%.
Be lower than at 0.2% o'clock and can't see significant stabilising effect by core matrix weight, and add the negative impact that stabilising effect when being higher than 5% antioxidant or reductive agent can be subjected to several factors; Some antioxidants and/or reductive agent have suction character, and this causes negative impact in high humidity environment.In addition, some salt have niff, and this smell will have a negative impact to end product when the high amount of ether is used.Even when making particle, the preparation of core matrix can comprise that with synthetic polymer with antioxidant and/or reductive agent and liquid, for example the enzyme concentrated solution mixes, and obtains more uniform mixture with two kinds of compounds that obtain solubilized form in core matrix.In some cases, see the synthetic polymer precipitation if the amount of antioxidant or reductive agent is when too high.
If antioxidant or reductive agent are added to the liquid that for example contains enzyme, the solubleness of antioxidant or reductive agent can be another limiting factor when preparing so.
Polysaccharide
Polysaccharide of the present invention can be not modified natural polysaccharide or the modified natural polysaccharide that exists of existing.
Suitable polysaccharide comprises Mierocrystalline cellulose, pectin, dextrin and starch.Starch dissolves in or is water insoluble.
In a particular of the present invention, polysaccharide is a starch.In a particular of the present invention, polysaccharide is an insoluble starch.
From various extensive plant origins natural exist starch in background of the present invention be suit (perhaps as starch itself, perhaps as the starting point of treated starch), relevant starch comprises from the starch of rice, corn, wheat, potato, oat, cassava, sago, yucca, barley, sweet potato, jowar, Chinese yam, rye, grain, buckwheat, arrowroot, taro, taro class, and can be the form of flour.
Tapioca (flour) is one of most preferred starch in background of the present invention; What can mention in this connection is that cassava and tapioca (flour) (Cassava starch) have multiple synonym, comprises tapioca, manioc, mandioca and manihot.
The term that uses in the context of the invention " treated starch " refers to native starch through some modification to small part chemically modified, enzyme modification and/or physics or physical chemistry modifying, and demonstrates the starch that has variation characteristic for " parent " starch usually.
The amount of the polysaccharide that uses in the matrix of the present invention especially is more than 2% of matrix by weight, more specifically by weight 2 to 75%, even more specifically by weight 2 to 50%, even more specifically by weight 5 to 30%, especially the most by weight 10 to 20%.
Too a large amount of polysaccharide can cause porous particle, thereby it has a negative impact to dust characteristic generation negatively influencing to the particulate rigidity.
The amount of starch of using in the matrix of the present invention by weight as matrix especially be higher than 2%, more specifically be higher than 5% by weight.
The amount of starch of using in the matrix of the present invention is 2 to 30% of matrix especially by weight, more specifically is higher than 2 to 20% by weight, especially the most by weight 5 to 15%.
We have found that as synthetic polymer or polysaccharide being added the alternatives of matrix or as a supplement other candidates likely with similar stabilization are nonactive albumen such as casein, albumin and gelatin and from the protein source of potato, rice, corn, corn steep liquor, wheat, soybean.
With the form of polysaccharide and/or protein adding matrix can be that enzymic fermentation liquid and/or enzyme reclaim mud, but can also add enzymic fermentation liquid and/or enzyme recovery mud except that polysaccharide and/or albumen.It is respectively from the residue behind enzymic fermentation step and the enzyme recycling step usually that enzymic fermentation liquid and enzyme reclaim mud.In a particular of the present invention, core matrix contains nonactive albumen, its can enzymic fermentation liquid and/or the enzyme form that reclaims mud add.
In an embodiment preferred of the present invention, core matrix contains:
A. active compound;
B. synthetic polymer, wherein the amount of the polymkeric substance of Jia Ruing is 0.1 to 10% of matrix by weight;
C. one or more antioxidants and/or reductive agent, wherein the amount of antioxidant and/or reductive agent is 0.2 to 5% of matrix by weight.
D. polysaccharide, wherein the amount of polysaccharide is more than 2% of matrix by weight.
In a particular of the present invention, synthetic polymer is PVP, and antioxidant is that Sulfothiorine and polysaccharide are starch.
We find that also by solvable inorganic salt are added in the matrix of the present invention, the matrix that contains active compound becomes more stable.
Inorganic salt:
Matrix can also contain solvable inorganic salt, and wherein said inorganic salt contain the divalent cation that is selected from zinc, magnesium and calcium, especially sal epsom and zinc sulfate.Preferred divalent cation is because they provide best preservation and processing stability.Vitriol is because it provides the optimum drying productive rate for preferred anionic surfactants.In a particular of the present invention, salt is sal epsom.
Also can use " dressing " (below) salt mentioned of part.
The salt amount of using in matrix of the present invention is 1 to 70% especially by weight, more specifically by weight 2 to 30%, especially the most by weight 2 to 10%.
The auxiliary matrix component:
Matrix can also contain the known conventional core material as the auxiliary matrix component, as wedding agent, solvent, weighting agent etc.These materials are described in WO 89/08694, WO 89/08695, EP 270608 B1 and/or WO 00/01793.Other examples of conventional coating material can be at US 4,106,991, EP 170360, EP 304332, EP 304331, EP 458849, EP 458845, WO97/39116, WO 92/12645A, WO 87/07292, WO 91/06638, WO 92/13030, WO 93/07260, WO 93/07263, WO 96/38527, WO 96/16151, WO 97/23606, US 5,324,649, US 4,689,297, EP 206417, EP 193829, DE 4344215, DE4322229 A, DD 263790, JP 61162185 A and/or JP 58179492 find.Other enzyme stabilizers that use can be boric acid and sodium tetraborate.
In a particular of the present invention, use core matrix of the present invention according to the notion of WO 01/25412, WO 01/25412 is incorporated herein by reference herein.
Core matrix can be randomly by dressing to prefabricated nuclear.
Prefabricated nuclear
Prefabricated nuclear also is known as carrier core, and blank nuclear (nuclear of non-activity compound) or seed are inert particles, contain the mixture of active compound can be on these inert particles form layers.Prefabricated two or more the composition that contains inorganic salt, sugar, sugar alcohol, little organic molecule such as organic acid or salt, mineral substance such as clay or silicate or they of endorsing.
In a particular of the present invention, can be applied to preparation nuclear on the prefabricated nuclear by the mixture that will contain active compound.
Dressing
Particle can contain one or more layers dressing.Coating thickness can for 1 μ to 1500 μ.In a particular, the thickness of dressing is greater than 30 μ, and in more specific embodiment, the thickness of dressing is greater than 50 μ, and in the most specific embodiment, coating thickness is greater than 75 μ.In a particular, coating thickness is less than 1000 μ, in more specific embodiment, the thickness of dressing is less than 500 μ, and in more specific embodiment, coating thickness is less than 250 μ, in the most specific embodiment, coating thickness is less than 150 μ.
We it has surprisingly been found that even by application of thin salt dressing, particulate stability has also increased, and by using the salt dressing, the life-span of antioxidant has prolonged.In a specific embodiment, particle contains thin salt dressing.
The salt dressing
Thickness is that the salt dressing of 2 to 5 μ demonstrates significantly improving of stability.In a particular of the present invention, the salt dressing is 2 to 30% of matrix and salt dressing by weight.In more specific embodiment, the amount of salt is 3 to 10% of matrix and salt dressing by weight.
The salt dressing can be for the other reasons of instability such as protection and integrity but thick dressing.
In a particular of the present invention, the thickness of salt dressing is that 1 μ is to 1000 μ.In more particular of the present invention, the thickness of salt dressing is that 2 μ are to 100 μ.In of the present invention even more specific embodiment, thick 3 μ of salt dressing are to 20 μ.
In a particular, the salt coating thickness is less than 500 μ.In a more specific embodiment, the salt coating thickness is less than 250 μ.In of the present invention even more specific embodiment, the salt coating thickness is less than 100 μ.In of the present invention even more specific embodiment, the salt coating thickness is less than 80 μ.In more specific embodiment of the present invention, the salt coating thickness is less than 50 μ.In the most specific embodiment, the salt coating thickness is less than 30 μ.
The salt dressing contains one or more salt.Salt can be a kind of inorganic salt, as vitriol, sulphite, phosphoric acid salt, phosphonate, nitrate, muriate or carbonate or simple organic acid salt (being less than 10 carbon) as 6 or still less carbon atom as Citrate trianion, malonate or acetate.Cationic example in these salt has basic metal or alkaline-earth metal ions, also can be the metal ion of the ammonium ion or first transition series, as sodium, potassium, magnesium, calcium, zinc or aluminium.Anionic example comprises chlorine, bromine, iodine, sulfate radical, inferior sulfate radical, bisulfite, thiosulfate anion, phosphate radical, the monobasic phosphate radical, the binary phosphate radical, the Hypophosporous Acid, 50 root, the dihydro pyrophosphate, the tetraboric acid root, borate, carbonate, bicarbonate radical, the metasilicic acid root, citrate, malate, maleate, malonate, amber acid radical, lactate, formate, acetate, the butyric acid root, propionate, the st-yrax acid group, tartrate anion, xitix root or glucose acid group.Especially, basic metal or alkaline earth metal sulphate, sulphite, phosphoric acid salt, phosphonate, nitrate, muriate or carbonate or simple organic acid salt such as Citrate trianion, malonate or acetate can be used.Specific example comprises NaH 2PO 4, Na 2HPO 4, Na 3PO 4, (NH 4) H 2PO 4, K 2HPO 4, KH 2PO 4, Na 2SO 4, K 2SO 4, KHSO 4, ZnSO 4, MgSO 4, CuSO 4, Mg (NO 3) 2, (NH 4) 2SO 4, Sodium Tetraborate, magnesium acetate and Trisodium Citrate.
Salt can be salt hydrate, promptly has the crystal salt hydrate of crystallization irreducible water, described at WO99/32595.The example of salt hydrate comprises bitter salt (MgSO 4(7H 2O)), Zinc vitriol (ZnSO 4(7H 2O)), Salzburg vitriol (CuSO 4(5H 2O)), seven hypophosphite monohydrate disodium hydrogen (Na 2HPO 4(7H 2O)), magnesium nitrate hexahydrate (Mg (NO 3) 2(6H 2O)), ten hydrated sodium borates, two hydration Trisodium Citrate and Magnesium diacetate tetrahydrates.
Extra dressing
The salt coated granules that contains matrix and choose wantonly can also be improved character so that particulate further to be provided by one or more layers coatings dressing.Can use conventional dressing as known in the art and method, as the dressing of in WO 89/08694, WO 89/08695,270 608 B1 and/or WO 00/01793, describing.Other examples of conventional coating material can be at US 4,106,991, EP 170360, EP 304332, EP304331, EP458849, EP 458845, WO 97/39116, WO 92/12645A, WO 89/08695, WO 89/08694, WO 87/07292, WO 91/06638, WO 92/13030, WO 93/07260, WO 93/07263, WO 96/38527, WO96/16151, WO 97/23606, US 5,324,649, US 4,689,297, EP 206417, EP 193829, DE 4344215, DE4322229 A, DD 263790, find among JP 61162185 A and/or the JP58179492.
Dressing can contain the material that is selected from the granulated materials of mentioning in wedding agent, fiber, salt, water soluble mineral substance, pigment, dyestuff, enzyme stabilizers or its combination and superincumbent " core " part.
Unfavorable compound
In the present invention, unfavorable compound is for finding to reduce the active compound of active compound.Unfavorable examples for compounds can be but be not limited to SYNTHETIC OPTICAL WHITNER, basic component, anion surfactant, metal chelator (for example builder).
The particulate preparation
The present invention also comprises preparation particulate method, and it comprises step:
A. prepare core matrix, wherein contain active compound, its amount and be 0.2 to 5% the component that is selected from antioxidant and reductive agent of core matrix by weight for 0.1 to 10% synthetic polymer of core matrix and its amount by weight;
B. one or more layers dressing is applied on the described core matrix.
Can prepare particle by technician's known method in the enzyme granulation field, these methods comprise that mixing tank granulation, fluidized bed coating, disk prilling granulator, dish bulge clothing, spraying drying, extruding, bed spray drying, high-shear are condensed, the combination of spheroidization or these technology.
The preparation of core matrix
Preparation core matrix particulate method comprises known enzyme granulate technology of preparing, for example spraying drying, fluidized-bed, bed spray drying, mixing tank granulation, dish drum technology and extruding.Other associated core particles are stratification product, adsorptivity product, become the ball product, become particulate product.Core can be chosen wantonly after granulation and be dried.
Following enzyme granulate technology of preparing can be used for the particulate preparation:
-spray-dired product wherein contains liquid the enzyme solution formation small droplets that atomizes in spray-drying tower, small droplets dry formation in the way that falls along drying tower containing the enzyme particulate matter.This method can be produced very little particulate (Michael S.Showell (editor); Powdered stain remover; Tensio-active agent science magazine (Surfactant Science Series); 1998; Vol.71; The 140-142 page or leaf; Marcel Dekker).
-layer-stepping product, wherein center on preformed inertia core particle bag by one deck enzyme, in this technology, typically in making prefabricated core particle fluidizing fluidized bed plant, to contain enzyme solution and atomize, and make again to contain that enzyme solution adheres on the core particle and dry up to forming dry enzyme layer on the core particle surface.Just can utilize this method to obtain the particulate of desired size if can access the useful core particle of desired size.To the explanation of this series products referring to as WO 97/23606.
-adsorptivity core particle, wherein be not around the core bag by one deck enzyme, but enzyme is adsorbed on the core surfaces and/or within.To the explanation of this method referring to WO 97/39116.
-extrude product or make the product of ball shape, wherein will contain the enzyme mashed prod and be pressed into piller, or under pressure, it is pressed through little perforate and be cut into particulate, carry out drying subsequently.Usually the size of this kind particulate is bigger, and this is can allow applied pressure to fall on the extruded hole because the material (plate that normally has boring) of preparation extruded hole has limited.In addition, if use little perforate, very high extruder pressure can make the heat generation in the enzyme mashed prod increase, and this is disadvantageous (Michael S.Showell (editor) to enzyme; Powdered stain remover; Tensio-active agent science magazine (Surfactant ScienceSeries); 1998; Vol.71; Page 140-142; Marcel Dekker).In a particular of the present invention, synthetic polymer and/or polysaccharide and/or protein source and/or antioxidant together mix with liquid such as enzyme enriched material or fermenting broth, then extruding.
-become granular product, wherein with the enzyme powder suspension in molten wax, and for example through spinning-disc atomizer, gained suspension sprayed enter cooling room, drop solidifies (Michael S.Showell (editor) rapidly in cooling room; Powdered stain remover; Tensio-active agent science magazine (Surfactant Science Series); 1998; Vol.71; Page 140-142; Marcel Dekker).In products obtained therefrom, enzyme is dispersed throughout in the whole inert material equably, rather than concentrates on its surface.Document US 4,016,040 and US 4,713,245 also relate to this technology.
-mixing granulation product, wherein add in the dry powder composite with conventional granulation composition containing enzyme liquid, liquid and powder mix with suitable proportion, and along with the moisture in the liquid is absorbed in the dry powder, each composition in the dry powder begins bonding cohesion, particulate increases, and has so just formed enzyme containing granule.US 4 is seen in the explanation of this method; 106; 991 (NOVO NORDISK) and pertinent literature EP170360 B1 (NOVO NORDISK); EP 304332 B1 (NOVO NORDISK); EP304331 (NOVO NORDISK); WO 90/09440 (NOVO NORDISK) and WO90/09428 (NOVO NORDISK). in the specific product that can utilize various high shear mixer as this method of nodulizer; can be with by enzyme; the particle that filler and tackiness agent etc. are formed mixes with cellulosic fibre to reinforce particulate; obtain so-called T-grain; more solid through the particulate of reinforcing, can discharge less enzyme dirt.
The method for preparing the memory fluid core particle is included in the method for describing among the WO 02/28991, and here the document is incorporated herein by reference.
In a particular of the present invention, synthetic polymer and/or polysaccharide and/or protein source and/or antioxidant and liquid for example enzyme concentrated solution or fermenting broth are mixed together then in the dressing chamber, for example fluidized-bed, multistage fluidized-bed, randomly have in the bed spray moisture eliminator of recirculation fine particle and be atomised on the prefabricated nuclear.
The preparation of salt dressing
By in fluidized-bed or bed spray moisture eliminator, the atomizing of salt dressing being applied to comprise on the particle of the matrix that contains active compound, the salt dressing also can be applicable to vacuum mixer, drage é type dressing machine (dish bulge clothing machine), be used for the equipment of seed pelleting, contain the equipment that rotates the end (as Roto Glatt, CFgranulators (Freund), torbed treater (Gauda) or rotating fluidized bed treater such as Omnitex (Nara).
After using salt deposit, particle can be chosen wantonly and be dried.Can pass through the available any drying means of technician, realize the drying of salt coated granule as spraying drying, lyophilize, vacuum-drying, fluidised bed drying, dish bulge clothing and microwave drying.The drying of salt coated granule also can make up with granulating method, and these granulating methods comprise and for example use fluidized-bed, bed spray drying (FSD) or multi stage drying device (MSD).
The preparation of extra dressing
Can use conventional dressing well known in the art and method aptly, as the dressing of in Denmark PA 200200473, WO 89/08694, WO89/08695,270 608 B1 and/or WO 00/01793, describing.Other examples of conventional coating material can be at US 4,106,991, EP 170360, EP304332, EP 304331, EP 458849, EP 458845, WO 97/39116, WO92/12645A, WO 89/08695, WO 89/08694, WO 87/07292, WO91/06638, WO 92/13030, WO 93/07260, WO 93/07263, WO 96/38527, WO 96/16151, WO 97/23606, WO 01/25412, WO 02/20746, WO 02/28369, US 5879920, US 5,324,649, US 4,689,297, US 6,348,442, EP 206417, EP 193829, DE 4344215, DE 4322229 A, DE 263790, find among JP 61162185 A and/or the JP 58179492.
Can be by preparing dressing with top " preparation of core matrix " and " preparation of salt dressing " method that part is identical.
Contain the composition and the application thereof of coated granule
The invention still further relates to and contain grains of composition of the present invention.Said composition can be any composition, but especially very suitable compositions such as cleaning compositions, textiles processing compositions, leather processing composition, paper pulp or paper conversion composition, food and drink composition, animal feedstuff compositions, pharmaceutical composition and personal care composition.
Cleaning compositions comprises stain remover and antimicrobial composition.The textiles processing compositions comprises the stone mill washing composition of the composition that is used for enzymatic bleach and/or textiles such as denim.Food and drink combinations be included in produce wine, oil ﹠ fat, oranges and tangerines and fruit juice product, starch and sugar product, alcohol and/or leavened prod, soybean prod and cure flour or dough/pasta industry in the enzymatic composition that uses.
The present invention also comprises the purposes of handling textiles, leather, paper pulp, paper, food, beverage, crust and human or animal's health.This particle also can be used for producing the medicine of handling the humans and animals body.
Stain remover
Coated particle of the present invention can also be added in the detergent compositions and therefore become its composition.
For example, detergent compositions of the present invention can be mixed with and be used to the clothing detergent compositions hand-washing or machine-wash, comprise the cleaning interpolation composition or the fabric softening compositions that are applicable to pre-treatment pollution fabric, or be used for the detergent compositions that the average family hard-surface cleaning is handled, or be applicable to the composition of craft or the operation of machine dishwashing.
A particular aspects, the invention provides the stain remover additive that contains coated particle of the present invention.Can comprise one or more other enzyme such as proteolytic enzyme in stain remover additive and the detergent compositions, lipase, at (Cutinase), amylase, carbohydrase, cellulase, polygalacturonase, mannase, arabanase, Galactanase, zytase, oxydase is as laccase and/or peroxidase.
In general, the character of selected enzyme should be compatible mutually with selected stain remover, and (be optimal pH, with the consistency of the component of other enzyme or non-enzyme etc.), and enzyme should exist with significant quantity.
Proteolytic enzyme: suitable proteolytic enzyme comprises animal, plant or microbe-derived proteolytic enzyme, the proteolytic enzyme in preferred microorganism source.Also comprise mutant chemically modified or protein engineeringization.Proteolytic enzyme can be serine protease or metalloprotease, especially alkaline microbial protease or trypsin-like proteolytic enzyme.The example of Sumizyme MP has subtilisin, especially derive from those of genus bacillus, as subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168 (explanation) referring to WO 89/06279. the example of trypsin-like proteolytic enzyme has trypsin as pig or Niu Yuan) and fusarium (Fusarium) proteolytic enzyme (to its description referring to WO 89/06270 and WO 94/25583).
The example of useful proteolytic enzyme is at WO 92/19729, and WO 98/20115, and the variant of describing among WO 98/20116 and the WO 98/34946 especially in one or more following sites the alternate variant takes place: 27,36,57,76,87,97,101,104,120,123,167,170,194,206,218,222,224,235 and 274.
Preferred business-like proteolytic enzyme comprises EVERLASE TM, OVOZYME TM, SAVOZYME TM, ALCALASE TM, SAVINASE TM, PRIMASE TM, DURALASE TM, ESPERASE TM, and KANNASE TM(Novozymes A/S), MAXATASE TM, MAXACAL TM, MAXAPEM TM, PROPERASE TM, PURAFECT TM, PURAFECT OXP TM, FN2 TM, and FN3 TM(Genencor International Inc.).
Lipase: suitable lipase comprises the lipase of bacterium and originated from fungus.Also comprise mutant chemically modified or protein engineeringization.The example of useful lipase comprises Humicola (Humicola) (synonym Thermomyces), the lipase of (as describing among EP 258 068 and the EP 305 216) H.lanuginosa (T.lanuginosus) or (as describing among the WO 96/13580) H.insolens; Rhodopseudomonas (Pseudomonas), as Pseudomonas alcaligenes (P.alcaligenes) or pseudomonas pseudoalcaligenes (P.pseudoalcaligenes) (EP 218 272), pseudomonas cepacia (P.cepacia) (EP 331 376), (GB 1 for Pseudomonas stutzeri (P.stutzeri), 372,034), Pseudomonas fluorescens (P.fluorescens), pseudomonas strain SD 705 (WO 95/06720 and WO96/27002), the lipase of P.wisconsinensis (WO 96/12012); Bacillus (Bacillus), as subtilis (B.subtilis) (Dartois etc. (1993), Biochemica etBiophysica Acta, 1131,253-360), bacstearothermophilus (B.stearothermophilus) (JP 64/744992) or bacillus pumilus (B.pumillus) lipase (WO91/16422).
Other example for example has at WO 92/05249, and WO 94/01541, and EP 407225, and EP 260105, WO 95/35381, and WO 96/00292, and WO 95/30744, and WO 94/25578, WO95/14783, WO 95/22615, the lipase Variant of describing among WO 97/04079 and the WO 97/07202.
Preferred business-like lipase comprises LIPOLASE TMWith LIPOLASE ULTRA TM(NovozymesA/S).
Amylase: suitable amylase (α and/or β) comprises the amylase of bacterium and originated from fungus.Also comprise mutant chemically modified or protein engineeringization.Amylase comprises that for instance, the α-Dian Fenmei of the specific bacterial strain of bacillus such as Bacillus licheniformis (B.lichenformis) describes in detail referring to GB 1,296,839.
Useful diastatic example has at WO 94/02597, and WO 94/18314, and the variant of describing among WO 96/23873 and the WO 97/43424 particularly in one or more following sites the alternate variant takes place:
15,23,105,106,124,128,133,154,156,181,188,190,197,202,208,209,243,264,304,305,391,408 and 444.
Business-like amylase has DURAMYL TM, TERMAMYL TM, FUNGAMYL TMAnd BAN TM(Novo zymes A/S), RAPIDASE TMAnd PURASTAR TMWith PURASTAR OXAM TM(from Genencor International Inc.).
Cellulase: suitable cellulase comprises the cellulase of bacterium and originated from fungus.Also comprise mutant chemically modified or protein engineeringization.Suitable cellulase comprises bacillus, Rhodopseudomonas, Humicola, fusarium (Fusarium), Thielavia (Thielavia), the cellulase of Acremonium (Acremonium), for example in US 4,435,307, US 5,648,263, US5,691,178, US 5,776,757 and WO 89/09259 in disclosed by Humicola insolens, the thermophilic fungal cellulase of ruining the generation of silk mould (Myceliophthora thermophila) and sharp sickle spore (Fusarium oxysporum).
Especially Shi Yi cellulase is to be of value to alkalescence and the neutral cellulase that color is safeguarded.The example of such cellulase has EP 0 495 257, and EP 0 531 372, and WO 96/11262, WO96/29397, the cellulase of describing among the WO 98/08940.Other example is just like at WO94/07998, and EP 0 531 315, and US 5,457,046, and US 5,686,593, and US 5,763,254, WO95/24471, the cellulase variants of describing among WO 98/12307 and the PCT/DK98/00299.
Business-like cellulase comprises CELLUZYME TM, and CAREZYME TM(Novozymes A/S), CLAZINASE TMAnd PURADAX HA TM(Genencor International Inc.), and KAC-500 (B) TM(Kao Corporation).
Peroxidase/oxydase: suitable peroxidase/oxydase comprises plant, and the peroxidase/oxydase of bacterium or originated from fungus also comprises mutant chemically modified or protein engineeringization.The example of useful peroxidase comprises the peroxidase of Coprinus (Coprinus) as Coprinus cinereus (C.cinereus), and variant, as at WO 93/24618, and those that describe among WO 95/10602 and the WO 98/15257.
Business-like peroxidase comprises GUARDZYME TM(Novozymes A/S).
Mannase: suitable mannase comprises MANNAWAY TM(NovozymesA/S).
Each independent additive that can contain one or more enzymes by interpolation, or comprise the combined additive of all these enzymes by interpolation, make to comprise these stain remover enzymes in the detergent compositions.Stain remover additive of the present invention, promptly additive or combined additive can be prepared by certain way separately, to make it to comprise the particulate of the present invention that one or more contain different enzymes.
Detergent compositions of the present invention can be taked any dried forms easily, as strip, and sheet sheet, powder, particle or paste.It can also be a liquid detergents, especially the non-aqueous liquid stain remover.
Detergent compositions can comprise one or more tensio-active agents, its can be non-ionic (comprising semi-polar) and/or anionic and/or cationic and/or zwitterionic tensio-active agent.The content of tensio-active agent generally is 0.1% to 60% by weight.
When comprising anion surfactant in the stain remover, stain remover comprises about 1% to about 40% anion surfactant usually, as linear alkylbenzene sulfonate, alpha-alefinically sulfonate, alkyl-sulphate (aliphatic alcohol sulfate), alcohol ethoxysulfate, secondary sulfonated alkane, alpha-sulfo fatty acid methyl ester, alkyl-or alkenyl Succinic Acid or soap.
When comprising nonionogenic tenside in the stain remover; stain remover contains 0.2% to about 40% the nonionogenic tenside of having an appointment, for example the N-acyl group N-alkyl derivative (" glucamide ") of ethoxylized fatty alcohol, ethoxylized nonylphenol, alkyl polyglycoside, alkyl dimethyl amine oxide, ethoxylated fatty acid single ethanol amide, fatty monoethanol amide, polyhydroxy alkyl fatty acid amide or glycosamine usually.
Stain remover can comprise stain remover builder or the complexing agent of 0-65%, for example zeolite, diphosphate, triphosphate, phosphoric acid salt, carbonate, Citrate trianion, nitrilotriacetic acid(NTA), ethylenediamine tetraacetic acid (EDTA), diethylene triaminepentaacetic acid(DTPA), alkyl-or alkenyl succinic, soluble silicate or stacked silicate (for example available from Hoechst SKS-6).
Stain remover can comprise one or more polymkeric substance.Example is carboxymethyl cellulose, poly-(V-Pyrol RC), poly-(ethylene glycol), poly-(vinyl alcohol), poly-(vinyl pyridine-N-oxide compound), poly-(vinyl imidazole), polycarboxylate such as polyacrylic ester, toxilic acid/acrylic copolymer and methacrylic acid bay alcohol ester/acrylic copolymer.
Stain remover can comprise bleaching system, and it can comprise H 2O 2Source such as perborate or percarbonate, and can make up with the bleach-activating agent that forms peracid such as tetra acetyl ethylene diamine or nonanoly acyloxy benzene sulfonate.In addition, bleaching system can comprise as acid amides, inferior acid amides, or the peroxy acid of sulfone type.
Enzyme in the detergent compositions of the present invention can pass through such as following conventional stablizer stable: polyvalent alcohol such as propylene glycol or glycerol, sugar or sugar alcohol, lactic acid, boric acid or boric acid derivatives such as fragrant boric acid ester or phenyl-boron dihydroxide derivative such as 4-formyl radical phenyl-boron dihydroxide, and described composition also can be by preparation described in WO 92/19709 and the WO 92/19708.
Described stain remover can also comprise other conventional stain remover composition, for example fabric conditioner (comprising clay), suds booster, froth suppressor, corrosion inhibitor, dirt suspension agent, the agent of anti-soil thing redeposition, dyestuff, sterilant, optical whitening agent, solubility promoter, tarnishing inhibitor or spices.
Think at present that in detergent compositions any enzyme can be being equivalent to the having 0.01-100mg zymoprotein in every liter of washings, the amount that has the 0.1-1mg zymoprotein in preferred every liter of washings 0.05-5mg zymoprotein, the especially every liter of washings adds.
In addition, enzyme of the present invention can add to as in the WO 97/07202 disclosed stain remover preparation, and the document is incorporated herein by reference hereby.
Embodiment
Embodiment 1
Proteolytic enzyme particle (the SAVINASE of dressing not TM) prepare by producer.
Prepare dust composition from following material (all percentage ratios provide with dried particulate %):
10% fibrous cellulose (Arbocel BC 200)
8% kaolin
5% dextrin (Avedex)
As the stabilizer component that provides in an embodiment
The tiny sodium sulfate of milling is added to 100%
They are mixed in L dige mixing tank and with proteolytic enzyme (SAVINASE TM) the ultrafiltrated spraying, it dissolves with 5% sugar and the stablizer that provide as embodiment.Moistening mixture is exposed to as at U.S. Patent number 4,106 compacting of describing among 991 the embodiment 1 and granulation influence.Particle is dry in fluidized-bed subsequently.
By 2% particle that produces is added in the stain remover and with in the weather cell of this sample retention in the opening beaker to measure enzyme granulate in different powder stain removers and the stability under the different condition.
Stability Design:
I:4 week 35 ℃/55%RH (low humidity) has the powder stain remover of bleaching
II:2 week 37 ℃/70%RH (high humidity) has the powder stain remover of bleaching
The powder stain remover of the non-bleaching of III 4 week 37 ℃/70%RH (high humidity)
The component that adds The % residual activity
Sulfothiorine % Starch rice % PVP％ ????I ???II ???III
????1 ????10 ??0 ??43.4 ??14.5 ??72.9
????1 ????10 ??2 ??45.8 ??29.9 ??95.0
How this embodiment increases stability in the high humidity environment if having illustrated PVP.
Embodiment 2
As embodiment 1 preparation particle.
The component that adds The % residual activity
Sulfothiorine % Starch rice % PVP％ ????I ????II ???III
????0 ????5 ??1 ??37.7 ???21.0 ???80.6
????2 ????5 ??1 ??53.3 ???23.1 ???93.0
This embodiment shows that Sulfothiorine is at low humidity with contain and increase stability in the environment of bleaching.
Embodiment 3
As embodiment 1 preparation particle.
The component that adds The % residual activity
Sulfothiorine % Starch rice % PVP％ ????I ????II ???III
????2 ????0 ??1 ????52.7 ???24.1 ???89.6
????2 ????10 ??1 ????60.4 ???29.4 ???93.1
This embodiment shows that polysaccharide such as Starch rice are at high and low-humidity environment and to contain in bleaching and the non-bleaching environment increase stable.
Embodiment 4
The preparation particle of describing as embodiment 1 and subsequently in fluidized-bed with 5% sodium sulfate dressing (being sprayed on the particle) by waterborne liquid with 28% sodium sulfate, 1% dextrin and 4% titanium dioxide composition.With particle also with as the wax dressing in WO 97/39116 embodiment 18, given.At last, with particle by fluidized-bed with 3%Sepifilm dressing (by the 15% Sepifilm LP030 aqueous solution from Seppic is sprayed on the particle).
Stability Design:
IV:8 week 35 ℃/55%RH (low humidity) has the powder stain remover of bleaching
V:2 week 37 ℃/70%RH (high humidity) has the powder stain remover of bleaching
The non-bleaching powder of VI:4 week 37 ℃/70%RH (high humidity) stain remover
The component that adds The % residual activity
Sulfothiorine % Potato albumen % Starch rice % PVP％ 5% salt dressing ??IV ??V ??VI
???2 ????5 ????5 ????1 Not ???61 ???30 ??61
???2 ????5 ????5 ????1 Be ???79 ???46 ??75
This embodiment has illustrated extra even thin salt dressing generally also improves stability.
Embodiment 5
Preparation particle as embodiment 1 describes still also uses the meticulous MgSO that mills 47H 2O rather than sodium sulfate is as weighting agent, and subsequently in fluidized-bed with 5% sodium sulfate dressing (being sprayed on the particle) by the waterborne liquid that 28% sodium sulfate, 1% dextrin and 4% titanium dioxide are formed.With particle also with as the wax dressing in WO 97/39116 embodiment 18, given.At last, with particle by fluidized-bed with 3%Sepifilm dressing (by the 15% Sepifilm LP030 aqueous solution from Seppic is sprayed on the particle).
The component that adds The % residual activity
Sulfothiorine % Potato albumen % Starch rice % PVP％ Weighting agent ??IV ???V ??VI
????2 ????5 ????5 ???1 ?Na 2SO 4 ???79 ???46 ???75
????2 ????5 ????5 ???1 ?MgSO 4 ???88 ???64 ???86
This embodiment shows MgSO 4General further enhanced stability.
Embodiment 6
As the preparation particle that provides among the embodiment 1, but also use Luviskol VA64 (from the V-Pyrol RC of BASF and 60/40 multipolymer of vinyl-acetic ester) as synthetic polymer.
Stability Design:
I:4 week 35 ℃/55%RH (low humidity) has the powder stain remover of bleaching
II:2 week 37 ℃/70%RH (high humidity) has the powder stain remover of bleaching
The non-bleaching powder of III:4 week 37 ℃/70%RH (high humidity) stain remover
The component that adds The % residual activity
Sulfothiorine % Potato albumen % Starch rice % Synthetic polymer % Synthetic polymer ????I ???II ??III
???2 ????5 ????5 ????0 ???- ??53.0 ??8.7 ??62.3
???2 ????5 ????5 ????1 ???PVP ??53.3 ??23.1 ??93.0
???2 ????5 ????5 ????1 ???VA64 ??53.6 ??18.2 ??88.0
Embodiment 7
As the preparation particle (promptly using 5% salt dressing) that in embodiment 4, provides, but do not use last Sepifilm and use rice and W-Gum.
Stability Design:
VII:12 week 35 ℃/55%RH (low humidity) has the powder stain remover of bleaching
The component that adds The % residual activity
Sulfothiorine % ????PVP％ Starch % Starch type ????VII
????2 ????1 ????10 Rice ????73
????2 ????1 ????10 Corn ????74
This embodiment shows other starch that can use outside the Starch rice.
Embodiment 8
Use different enzyme types, as preparation particle as described in the embodiment 7 (but promptly use 5% salt dressing without Sepifilm).
Stability Design:
The powder stain remover of the non-bleaching of VIII:8 week 37 ℃/70%RH (high humidity)
The component that adds The % residual activity
The enzyme type Sulfothiorine % Starch rice % ??PVP ??％ 5% salt dressing ????V ??VI ???VII ??VIII
Spill Wei Naisi (proteolytic enzyme) ????0 ????0 ???0 Not ????13 ????- ????26 ????59
Spill Wei Naisi (proteolytic enzyme) ????2 ????10 ???1 Be ????28 ????- ????60 ????89
Amylase ????0 ????0 ???0 Not ????2 ????40 ????0 ????-
Amylase ????2 ????10 ???1 Be ????8 ????73 ????47 ????-
Lipase ????0 ????0 ???0 Not ????12 ????- ????12 ????17
Lipase ????2 ????10 ???1 Be ????23 ????- ????40 ????20
Cellulase ????0 ????0 ???0 Not ????7 ????- ????22 ????-
Cellulase ????2 ????10 ???1 Be ????7 ????- ????56 ????-
This embodiment shows that stable system is all effective to different enzyme types.

Claims (27)

1. contain core matrix and one or more layers coated granules, wherein core matrix comprises:
A. active compound;
B. synthetic polymer, wherein the amount of the polymkeric substance of Jia Ruing is 0.1 to 10% of core matrix by weight;
C. be selected from one or more components of antioxidant and reductive agent, wherein the amount of antioxidant and reductive agent is 0.2 to 5% of core matrix by weight.
2. according to the particle of claim 1, its mesostroma also comprises polysaccharide, and wherein the amount of polysaccharide is more than 2% of core matrix by weight.
3. according to the particle of claim 1, wherein the amount of synthetic polymer is 1 to 2% by weight in the core matrix.
4. according to the particle of claim 1, wherein the amount of antioxidant and reductive agent is 1 to 3% by weight in the core matrix.
5. according to the particle of claim 1, wherein active compound is an enzyme.
6. according to the particle of claim 1, wherein synthetic polymer is polyethylene polymer and the multipolymer thereof that is selected from PVP, PVA.
7. according to the particle of claim 1, wherein antioxidant or reductive agent are selected from Sulfothiorine, S-WAT, thio-2 acid, erythorbate, ascorbate salt or methionine(Met).
8. according to the particle of claim 1, wherein synthetic polymer is that PVP and antioxidant are Sulfothiorine.
9. according to the particle of claim 2, wherein the amount of polysaccharide is 2 to 75% by weight in the core matrix.
10. according to the particle of claim 2, wherein polysaccharide is a starch.
11. according to each particle of front claim, wherein core matrix by dressing on prefabricated core.
12. according to each particle of front claim, it also comprises sal epsom or Magnesium sulfate heptahydrate.
13. according to the particle of claim 12, wherein the amount of the sal epsom of Jia Ruing is 1 to 70% of core matrix by weight.
14. according to each particle of front claim, wherein particle salt deposit dressing.
15. according to the particle of claim 14, wherein salt deposit is 2% to 30% of core matrix and salt deposit by weight.
16. according to the particle of claim 14, wherein salt deposit is 3 to 10% of core matrix and salt deposit by weight.
17. according to the particle of claim 14, salt bed thickness 2 to 100 μ wherein.
18. according to each particle of front claim, it also includes the protectiveness dressing.
19. preparation particulate method, it comprises step:
A. preparation comprise active compound, by weight for 0.1 to 10% synthetic polymer of core matrix be the core matrix of 0.2 to 5% the component that is selected from antioxidant and reductive agent of core matrix by weight;
B. one or more layers dressing is applied to described core matrix.
20. according to the method for claim 19, wherein particle prepares in mixing tank, fluidized-bed, bed spray moisture eliminator, spray-dryer or extrusion machine.
21. according to the method for claim 19, wherein particle is dried.
22. composition, it comprises each particle of claim 1 to 21.
23. the composition of claim 22, wherein composition is selected from cleaning compositions, textiles processing compositions, leather processing composition, paper pulp or paper conversion composition, food and drink composition, animal feedstuff compositions, personal care composition and pharmaceutical composition.
24. the foodstuffs compositions of claim 23, wherein foodstuffs compositions is for curing flour.
25. the foodstuffs compositions of claim 23, wherein said composition is a dough/pasta.
26. the cleaning compositions of claim 23, wherein said composition is a stain remover.
27., be used to handle the object that is selected from crust, textiles, leather, paper pulp, paper, food, beverage and human or animal's health according to each particulate purposes of claim 1 to 26.
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WO2004003188A3 (en) 2004-02-26
WO2004003188A2 (en) 2004-01-08

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