EP1220885B1 - Particules pour compositions liquides - Google Patents

Particules pour compositions liquides Download PDF

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Publication number
EP1220885B1
EP1220885B1 EP00960378A EP00960378A EP1220885B1 EP 1220885 B1 EP1220885 B1 EP 1220885B1 EP 00960378 A EP00960378 A EP 00960378A EP 00960378 A EP00960378 A EP 00960378A EP 1220885 B1 EP1220885 B1 EP 1220885B1
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EP
European Patent Office
Prior art keywords
wax
particle
particles
enzyme
solid
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Expired - Lifetime
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EP00960378A
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German (de)
English (en)
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EP1220885A1 (fr
Inventor
Ole Regnar Hansen
Erik Marcussen
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Novozymes AS
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Novozymes AS
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • This invention relates to an active containing particle of a construction which makes it suitable for incorporation in liquid compositions. Furthermore the invention relates to processes for manufacturing active containing particles and liquid compositions, such as liquid detergents, comprising the active containing particle. The invention also relates to the use of the active containing particles and liquid compositions comprising the active containing particle.
  • Detergent products in the form of liquid are often considered to be more convenient to use than are dry powdered or particulate detergent products. Said detergents have therefore found substantial favour with consumers. Such detergent products are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and are non-dusting. They also usually occupy less storage space than granular products. Additionally, such detergents may have incorporated in their formulations materials which could not withstand drying operations without deterioration, which operations are often employed in the manufacture of particulate or granular detergent products.
  • detergents have a number of advantages over granular detergent products, they also inherently possess several disadvantages.
  • detergent composition components which may be compatible with each other in granular products may tend to interact or react with each other.
  • components such as enzymes or other actives can be especially difficult to incorporate into liquid detergent products while maintaining an acceptable degree of stability of the enzymes.
  • Solid enzyme containing particles are known to the art from various disclosures as well as their use in dry powder detergents. See for examples: Michael S. Showell (editor); Powdered detergents; Surfactant Science Series; 1998; vol. 71; page 140-142; Marcel Dekker.
  • One object of the invention is to provide liquid compositions comprising an active in which the active is protected from being inactivated from other components of the composition or in which the active in inhibited in inactivating other components of the composition.
  • this may be achieved by incorporating the active in solid particles which may be dispersed in liquid compositions.
  • it is important to inhibit sedimentation, agglomeration or other forms of mechanisms which may concentrate the particles in specific parts or layers of the liquid composition incorporating the particles.
  • a further object of the invention is to provide particles, which may be dispersed in a liquid composition, wherein the dispersion stability is improved.
  • a still further object of the invention is to provide a good method for producing particles suitable for incorporating an active and in which the properties of the resulting particles may easily be adjusted to fit the properties of the liquid into which the particles are to be dispersed so as to improve the dispersion stability of the particles in the liquid composition.
  • the invention relates to liquid compositions having dispersed in a liquid phase solid particles, wherein the solid particles comprises a solid wax matrix in which an active, preferably in solid particulate form, is distributed.
  • the invention also relates to a particle comprising a solid matrix of a mixture of at least two solid waxes wherein an active, preferably in solid particulate form is distributed.
  • the invention further relates to a particle comprising a solid matrix wherein an active, preferably in solid particulate form and a density modifier is distributed.
  • the invention relates to processes for preparing liquid compositions of the invention and processes for preparing particles of the invention and use of liquid compositions and particles of the invention.
  • the present invention offers several advantages: It is possible to prepare particles having a narrow size distribution and a very uniform true density of the particles.
  • a narrow size distribution of enzyme containing particles has conventionally been desired because the true density of known particles varies with size of the particles. However with increasing uniformness of the particles true density, the size distribution becomes less important as the differences in true density between smaller and larger particles diminish.
  • the true density of the particles may be adjusted to suit the density of the liquid in which the particles are to be dispersed and thereby enabling dispersions of particles in the liquid with an improved dispersion stability.
  • the chemical and/or physical stability of the active may be improved by incorporating the active in a solid wax matrix in stead of adding the active to the liquid composition without being incorporated in the particle of the invention.
  • any hazards, such as dusting, toxicity and the like, in handling the active prior to forming a liquid dispersion, e.g. when the active is in pure dry form, may be lowered by incorporating the active in a wax matrix and may be further improved through coating the particle with a coating layer free of active.
  • true density of a compound as used herein is to be construed as the density in weight per volume of said compound, determined by immersing a weighed amount of the compound in a liquid in which the compound is insoluble and measuring the volume increase of liquid dispersion (i.e. the volume of liquid which is displaced by the compound).
  • the volume increase of liquid dispersion i.e. the volume of liquid which is displaced by the compound.
  • 1 gram of a compound is added to a volume of 10 cm 3 of a liquid in which the compound is insoluble and by said addition the volume of the liquid-compound mixture increases to 11 cm 3 , the compound thereby displacing 1 cm 3 of liquid, the true density of the compound is 1 gram per cm 3 .
  • the true density of a liquid may be measured as the weight of a measured volume of the liquid.
  • wax as used herein, is to be construed as a compound having a melting point between 25-150 °C.
  • solid wax matrix is to be construed as a wax in a solid particulate phase, wherein enzymes and other useful components are distributed, and wherein the wax is used for tying and/or binding the other components together to form a solid discrete and particulate entity.
  • the wax or mixture of waxes constituting the wax matrix constitutes at least 35% w/w of the particle in which the active and other useful components are distributed.
  • distributed as used herein concerning actives being distributed in a wax matrix for is to be understood as the active being evenly or homogeneously present throughout the wax matrix e.g. as active dissolved in the wax and/or as discrete clusters or particles of active homogeneously dispersed in the wax.
  • the particle containing an active as provided by the invention comprises a solid wax matrix and an active, preferably in solid particulate form and optionally other useful components, which are different from the wax and the active, distributed in the solid wax matrix and the particle is optionally coated with one or more coating layers.
  • the particle components including the coating materials are preferably dispersible or soluble in aqueous solutions containing more than 50% w/w water at neutral to alkaline pH.
  • Useful particle sizes lies within the range of about 20 ⁇ m to about 2000 ⁇ m, preferably between about 100 ⁇ m to about 1000 ⁇ m, e.g. between about 200 ⁇ m to about 600 ⁇ m.
  • the true density of the particles is between about plus 0.5 g/cm 3 to about minus 0.5 g/cm 3 of the true density of the liquid phase in which the particles are to be dispersed in. That means that if the liquid phase has a true density of for example 2 g/cm 3 the true density of the particle should be between about 1.5 g/cm 3 to about 2.5 g/cm 3 . Of course smaller difference between the true densities of the particles and the liquid phase are better, so preferably the true density of the particles lies between about plus 0.3 g/cm 3 to about minus 0.3 g/cm 3 , e.g. between about 0.1 g/cm 3 to about minus 0.1 g/cm 3 of the true density of the liquid phase.
  • the difference in true density between the particles and the liquid phase may be bigger depending on the viscosity of the liquid phase.
  • true density of the particles may be outside the range of the true density of the liquid plus or minus 0.5 g/cm 3 .
  • particles of a size such as between 50 ⁇ m to 200 ⁇ m may have a true density e.g. in the ranges plus or minus 0.5- 1.5 g/cm 3 of the true density of the liquid phase.
  • the particle of the invention comprises, in one aspect of the invention, a solid wax matrix wherein an active is distributed.
  • a wax is a compound, which have a melting point between 20-150 °C.
  • Preferred waxes are organic compounds or salts of organic compounds having a melting point in the said range.
  • the solid wax matrix may be any wax or mixture of waxes suitable for the purpose of incorporating the finished particle in a liquid composition.
  • the term "wax" as used herein also encompasses mixtures of two or more different waxes. Mixture of different waxes, optionally in combination with heavy and/or light solids are preferred because by mixing waxes of different properties and optionally mixtures of heavy and light solids, particles of a desired true density can be obtained. Accordingly the invention provides a particle comprising a mixture of at least two waxes. Also encompassed by the invention are enzyme particles comprising a mixture of 3, 4 or even 5 waxes.
  • the wax should be water soluble or water dispersible, preferably in neutral and alkaline solution, so that when the liquid composition of the invention is introduced into an aqueous solution, i.e. by diluting it with water, the solid wax matrix of the particle should disintegrate and/or dissolve providing a quick release and dissolution of the active incorporated in the particles to the aqueous solution.
  • water soluble waxes are poly ethylene glycols (PEG's) Accordingly amongst water soluble waxes the solubility of wax in water should preferably be up to 75 parts wax to 25 parts water, such as for PEG 1000.
  • PEG poly ethylene glycols
  • the solubility of wax in water should preferably be up to 75 parts wax to 25 parts water, such as for PEG 1000.
  • water insoluble waxes which are dispersible in an aqueous solution are triglycerides and oils.
  • substantially nonaqueous in this context may be defined as the liquid phase containing little (e.g. below 5 % w/w or below 3% w/w) or no water (non-aqueous). Water, if any, present in the nonaqueous liquid of the invention is preferably present due to inclusion of hydrated compounds.
  • the wax should also be compatible with the active, i.e. it should not inactivate the active, e.g. by reacting with the active or permanently altering structures, such as, in case of polypeptides, foldings, helical portions, sheeted portions, prosthetic groups and the like necessary for the active to retain the activity.
  • the wax should be mixable with the active, i.e. the active may be dissolved in the (molten) wax and/or the active may be dispersed in the (molten) wax in an dry particulate form such as particles of amorphous and/or crystalline protein, peptide and/or polypeptide.
  • the wax of the invention is in a solid state at room temperature (25°C), and accordingly is has a melting point or a melting range (polymer waxes tend to melt over a range of temperatures) above this temperature.
  • a preferred wax has a melting point or range between about 35°C to about 120°C.
  • the lower limit is preferred to set a reasonable distance between the temperature at which the wax melts to the temperature at which liquid compositions comprising the particles are usually stored (20-30°C). Also, difficulties are contemplated, in the manufacture of the particles when the melting point of the wax is below 35 °C.
  • the upper temperature limit is set as the maximum temperature usually applicable for actives without experiencing significant losses of activity, due to e.g. heat denaturation.
  • a more preferred melting point or range is between about 40°C to about 100°C, such as between about 50°C to about 80°C.
  • the true density of the wax itself between about plus 0.5 g/cm 3 to about minus 0.5 g/cm 3 of the true density of the liquid in which the finished particle is to be dispersed, preferably between about plus 0.3 g/cm 3 to about minus 0.3 g/cm 3 , e.g. between about 0.1 g/cm 3 to about minus 0.1 g/cm 3 .
  • the true density of the wax or mixture of waxes is preferably lower than 1.4 g/cm 3 , more preferably lower than 1.2 g/cm 3 , most preferably lower than 1.1 g/cm 3
  • the true density of the finished particle is important, and accordingly the true density of the wax may be considerably higher or lower than the liquid phase if the particles are small, such as between 50-200 ⁇ m, or other components which may be comprised in the particle compensate to adjust the true density of the particles.
  • the wax of the invention have a molecular weight between about 150 Daltons to about 10.000 Daltons.
  • the wax of the invention may be any wax, which is chemically synthesized. It may also equally well be a wax isolated from a natural source or a derivative thereof. Accordingly in the wax of the invention is preferably selected from the following non limiting list of waxes.
  • waxes which are useful in the invention can be found in C.M. McTaggart et. al., Int. J. Pharm. 19, 139 (1984) or Flanders et.al., Drug Dev. Ind. Pharm. 13, 1001 (1987) both incorporated herein by reference.
  • the amount of wax in an un-coated enzyme containing particle is at least 35% w/w in order for the wax to constitute a solid matrix as well as secure suitable pumping and atomization properties (cf. below).
  • a preferred amount of wax is at least 50 % w/w such as at least 75% w/w.
  • the active of the invention may any active component or mixture of active components which benefits from being separated from the liquid phase of a liquid composition.
  • active is meant to encompass all components which upon release from the wax matrix upon applying the composition or particle of the invention in a process serves a purpose of improving the process. Suitable actives are those which are either subjects of deactivation and/or causing deactivation to other components in the compositions of the invention. As said the active is preferably present dispersed as discrete solid particles in the solid wax matrix. Providing the active in solid for instead of dissolved in the wax may provide more freedom to choose different waxes and it may also provide improved stability of the active.
  • the active may be inorganic of nature such as bleach components as mentioned infra or organic.
  • Preferred actives are active biological materials which are usually very sensitive to the surrounding environment, such as materials obtainable from microorganisms.
  • Most preferred actives are peptides or polypetides such as enzymes.
  • the enzyme in the context of the present invention may be any enzyme or combination of different enzymes, which benefits from being incorporated in a particle when comprised in a liquid detergent. 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.-.-.-), ligases (EC 6.-.-.-) and mannanases.
  • Preferred oxidoreductases in the context of the invention are peroxidases (EC 1.11.1), laccases (EC 1.10.3.2) and glucose oxidases (EC 1.1.3.4)].
  • An Example of a commercially available oxidoreductase (EC 1.-.-.-) is Gluzyme TM (enzyme available from Novo Nordisk A/S). Further oxidoreductases are available from other suppliers.
  • Preferred transferases are transferases in any of the following sub-classes:
  • a most preferred type of transferase in the context of the invention is a transglutaminase (protein-glutamine ⁇ -glutamyltransferase; EC 2.3.2.13) .
  • transglutaminases are described in WO 96/06931 (Novo Nordisk A/S).
  • Preferred hydrolases in the context of the invention are: Carboxylic ester hydrolases (EC 3.1.1.-) such as lipases (EC 3.1.1.3); phyrases (EC 3.1.3.-), e.g. 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”), such as ⁇ -amylases (EC 3.2.1.1); peptidases (EC 3.4, also known as proteases); and other carbonyl hydrolases].
  • Carboxylic ester hydrolases EC 3.1.1.-
  • lipases EC 3.1.1.3
  • phyrases EC 3.1.3.-
  • 3-phytases e.g. 3-phytases
  • 6-phytases EC 3.1.3.26
  • glycosidases EC 3.2, which fall within a group denoted herein as "carbo
  • carbohydrase is used to denote not only enzymes capable of breaking down carbohydrate chains (e.g. starches or cellulose) of especially five- and six-membered ring structures (i.e. glycosidases, EC 3.2), but also 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), glucan 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), polygalacturonases (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), amylo-1,6-glucos
  • proteases examples include Kannase TM , Everlase TM , Esperase TM , Alcalase TM , Neutrase TM , Durazym TM , Savinase TM , Pyrase TM , Pancreatic Trypsin NOVO (PTN), Bio-Feed TM Pro and Clear-Lens TM Pro (all available from Novo Nordisk A/S, Bagsvaerd, Denmark).
  • proteases include Maxatase TM , Maxacal TM , Maxapem TM , Opticlean TM and Purafect TM (available from Genencor International Inc. or Gist-Brocades).
  • lipases examples include Lipoprime TM Lipolase TM , Lipolase TM Ultra, Lipozyme TM , Palatase TM , Novozym TM 435 and Lecitase TM (all available from Novo Nordisk A/S) .
  • lipases include Lumafast TM (Pseudomonas mendocina lipase from Genencor International Inc.); Lipomax TM (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-Gal TM , Bio-Feed TM Alpha, Bio-Feed TM Beta, Bio-Feed TM Plus, Bio-Feed TM Plus, Novozyme TM 188, 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 , AMGTM (Amyloglucosidase Novo), Maltogenase TM , Sweetzyme TM and Aquazym TM (all available from Novo Nordisk
  • the content of enzyme (calculated as pure enzyme protein) in a particle of the invention will typically be in the range of from about 0.05% to 50% by weight of the enzyme-containing particle.
  • protease peptidase
  • the enzyme activity (proteolytic activity) of the finished granules will typically be in the range of 1-20 KNPU/g.
  • This unit for protease activity is K ilo N ovo P rotease U nits per gram of sample (KNPU/g).
  • the activity is determined relatively to an enzyme standard of known activity in KNPU/g.
  • the enzyme standard is standardized by measuring for a given amount of enzyme the formation rate ( ⁇ mol/minute) of free amino groups liberated from digestion of di-methyl-casein (DMC) in solution by the enzyme.
  • the formation rate is monitored by recording the linear development of absorbance at 420 nm of the simultaneous reaction between the formed free amino groups and added 2,4,6-tri-nitro-benzenesulfonic acid (TNBS).
  • TNBS 2,4,6-tri-nitro-benzenesulfonic acid
  • the digestion of DMC and the color reaction is carried out at 50°C in a pH 8.3 boric acid buffer with a 9 min. reaction time followed by a 3 min. measuring time.
  • a folder AF 220/1 is available upon request to Novo Nordisk A/S, Denmark, which folder is hereby included by reference.
  • an activity of 10-500 KNU/g will be typical.
  • the activity is determined relatively to an enzyme standard of known activity in KNU/g.
  • the enzyme standard is standardized by measuring for a given amount of enzyme the formation rate ( ⁇ mol/minute) of 2-chlor-4-nitrophenol liberated from digestion of 2-chlor-4-nitrophenyl-b-D-maltoheptaosid substrate by the enzyme and auxiliary alfa- and beta-glucosidase enzymes in solution. Kits for performing ⁇ -amylase assays are commercially available.
  • ⁇ -amylase assay may be found in the leaflet AF318/1-GB available upon request from Novo Nordisk A/S, Denmark.
  • an activity in the range of 50-400 KLU/g will normally be suitable.
  • the particles of the invention may, as said, also contain one or more other components, which is different from the active and the wax. These components should preferably also be dispersible or soluble in aqueous solution at neutral or alkaline pH.
  • the term "different” as used in this context is to be understood as a component is not identical to the active nor to the wax.
  • Other components may be divided into components which are used to modify the true density of the particle (herein denoted a "density modifier") and components which provides other properties to the particle.
  • Density modifiers as used herein is defined as components which has a lower or higher true density than the wax matrix.
  • the density modifier is preferably a solid or a gas dispersed in the wax matrix.
  • a preferred density modifier is a light component useful for lowering the true density of the particle of the invention.
  • a light component have a true density lower than the true density of the solid wax matrix thus enabling adjustment of the true density of the finished particle.
  • the true density of the light component is at least 0.2 g/cm 3 lower than the true density of the solid wax matrix incorporating the enzyme, preferably at least 0.4 g/cm 3 lower, e.g. at least 0.6 g/cm 3 lower than the solid wax matrix incorporating the enzyme.
  • Light weight components may be selected from following non-limiting list:
  • the density modifier is a heavy component useful for adjusting the true density of the particle of the invention.
  • a heavy component have a true density higher than the true density of the solid wax matrix incorporating the enzyme thus enabling adjustment of the true density of the finished enzyme particle.
  • the true density of the light material is at least 0.2 g/cm 3 higher than that of the solid wax matrix incorporating the enzyme, preferably at least 0.4 g/cm 3 higher, e.g. at least 0.6 g/cm 3 higher than the solid wax matrix incorporating the enzyme.
  • Heavy material may be selected from following non-limiting list:
  • the particles may suitably be coated with one or more coating layers surrounding the solid wax matrix comprising the active, which also may provide additional protection of the active from components in the surrounding environment, e.g. liquid phase.
  • the invention also provides particles of the invention coated with one or more coating layers surrounding the solid wax matrix.
  • the coating is preferably substantially free of active, e.g. the coating contains less than 6 milligram active, such as enzyme per gram coating.
  • one or more layers of coating which may comprise additional actives may be applied between the wax matrix particle and the outer coating layer.
  • Useful coatings for particles of the invention are described in the art, such as in the international patent application DK99/00364 (unpublished).
  • the coating also comprises a wax such as described, supra.
  • coating materials may be chosen which is soluble or dispersible in the liquid phase of the liquid composition.
  • the coating material is insoluble or indispersible in the liquid phase of the liquid composition and in a second preferred embodiment the coating material is soluble or dispersible in the liquid phase of the liquid composition.
  • the coating may be applied by conventional coating methods e.g. in a mixer granulator or a fluid bed e.g. by spraying the coating material or a solution or dispersion thereof onto the particles of the invention.
  • the invention also relates to processes for preparing particles of the invention.
  • a process comprising step (a) is preferred while in a further embodiment a process comprising step (b) is preferred, while in a still further embodiment a process comprising step (c) is preferred.
  • the invention also encompasses products obtainable by a process comprising steps (a), (d) and (e) or (b), (d) and (e) or (c), (d) and (e).
  • step (e) are preferably performed in a so-called spray-cooling or spray-chilling process as known to the art, comprising the steps of:
  • the active may be applied to the molten wax by mixing a preferably purified solid active into the molten wax.
  • the active being an enzyme
  • the enzyme is preferably a crystalline or amorphous enzyme preparation (such as described in WO 91/09943).
  • the active and optionally other components are in a dry powder form such as spray dried products, which is dispersed or suspended in the molten wax.
  • Atomization of the molten wax may be achieved in a number of way, where amongst it is preferred to perform the atomization using either a high speed rotating disk atomizer, a pressure nozzle, a pneumatic nozzle or a sonic nozzle such as described in the Course Material from the Micro-encapsulation Seminar, held by Center for professional advancement on May 9 to May 11, 1990 in Amsterdam.
  • the solidification of the droplets by cooling may advantageously be performed in a cooling container such as a tower, wherein the atomized dispersion or solution of enzyme in molten wax is introduced into a cold air stream in the top of the tower, and the solidification of the droplets occurs while the droplets passes through the cold air stream towards the bottom of the tower.
  • the mixture of molten wax, enzyme and optionally other components is preferably fed to the atomizer at a temperature at least 30 °C above the temperature at which the solidification commences, in order to avoid unintended solidification and blockage in feed pipes and atomizer.
  • the quantity and temperature of air used for cooling the molten wax mixture should be adjusted so that is able of removing sufficient heat from the molten wax mixture to enable solidification (sensible heat of the liquid, latent heat of fusion of the solid and sensible heat of the solid).
  • the temperature of air leaving the cooling tower (figure 1 D) is about 5°C below the temperature of solid particles leaving the cooling tower.
  • very spherical particles may be achieved of a size, which may be adjusted by adjusting the atomization and cooling conditions.
  • Useful particle sizes lies within the range of about 20 ⁇ m to about 2000 ⁇ m, preferably between about 100 ⁇ m to about 1000 ⁇ m, e.g. between about 200 ⁇ m to about 600 ⁇ m.
  • particles with a narrow size distribution may be prepared, lowering the need for separating, e.g. by sieving, and recycling over- and undersized particles.
  • the particles have, prior to a sieving and/or recycling step, a SPAN value below about 2.0 preferably below about 1.2, more preferably below about 1.0, more preferably below about 0.8 and most preferably below about 0.6.
  • the SPAN value is a measure of the breadth the particle size distribution (PSD) and is defined as: ( D 90 - D 10 ) / D 50 wherein the D values expresses the mass mean diameter of the individual particles.
  • the mean mass diameter, D50 is the diameter at which 50% of the enzyme particles, by mass, have a smaller diameter, while 50% by mass have a larger diameter.
  • the values D10 and D90 are the diameters at which 10% and 90%, respectively, of the particles, by mass, have a smaller diameter than the value in question. The smaller the SPAN value is, the narrower the particle size distribution is.
  • the particle size distribution is normally as narrow as possible.
  • the span of a granulate product according to the invention is therefore typically not more than about 2.5, preferably not more than about 2.0, more preferably not more than about 1.5, and most preferably not more than about 1.0.
  • the invention also encompasses the preferred process of particles being prepared by making a dispersion of active and optionally other components in one or more molten waxes, letting the wax(es) solidify and milling/crushing the solid wax matrix into particles and optionally rounding the particles, e.g. in a Marumerizer, before optionally coating the particles.
  • Coating of the prepared enzyme containing particles may be achieved by any conventional coating method, such as in a fluid bed coater, the process comprising:
  • the invention also relates to a liquid composition comprising dispersed herein solid particles of the invention, as described supra . Also encompassed by the invention is a process for preparing a liquid composition comprising the step of dispersing solid particles of the invention in a liquid phase.
  • the liquid phase of the composition is in a liquid form at 20°C.
  • the particles of the invention is substantially stably dispersed in the liquid phase of the composition.
  • substantially stable dispersion of particles in a liquid composition is defined as a dispersion wherein separation of the particles from the liquid phase, whereby the particles concentrates in a portion of the composition cannot be visually observed on a sample of the dispersion kept at 20°C for at least 48 hours.
  • a separation of separation of the enzyme particles from the liquid phase cannot be observed on a sample of the dispersion kept at 20°C for at least one, more preferably two weeks.
  • the active in the particle is an enzyme and the liquid composition is a liquid detergent composition.
  • the liquid composition is a liquid detergent composition.
  • the enzyme particle In order for an enzyme particle to stay dispersed in a liquid detergent phase one important property of the particle is its true density. If the enzyme particle have a true density which significantly exceeds the true density of the liquid detergent phase the enzyme particle will over time not stay dispersed in the liquid detergent phase, but affected by gravitational forces it will move towards the bottom of the liquid phase and form an enzyme particle sediment. If however the true density of the enzyme particles is significantly less than the true density of the liquid detergent phase the enzyme particles will concentrate at the surface. It is contemplated, that these movements are of course dependent of the viscosity of the liquid phase in which the particles are dispersed and the size of the particles, i.e.
  • the liquid detergent composition of the invention comprises enzyme particles, which have a true density between about plus 0.5 g/cm 3 to about minus 0.5 g/cm 3 of the true density of the liquid detergent phase. That means that if the detergent has a true density of for example 2 g/cm 3 the true density of the enzyme particle should be between about 1.5 g/cm 3 to about 2.5 g/cm 3 .
  • the true density of the enzyme particles lies between about plus 0.3 g/cm 3 to about minus 0.3 g/cm 3 , e.g. between about 0.1 g/cm 3 to about minus 0.1 g/cm 3 of the true density of the liquid detergent phase.
  • the difference in true density between the enzyme particles and the liquid phase may be bigger depending on the viscosity of the liquid phase.
  • true density of the particles may be outside the range of the true density of the liquid plus or minus 0.5 g/cm 3 .
  • particles of a size such as between 50 ⁇ m to 200 ⁇ m may have a true density e.g. in the ranges plus or minus 0.5-1.5 g/cm 3 of the true density of the liquid phase.
  • the liquid detergent composition of the invention is preferably substantially non-aqueous (or anhydrous) in character.
  • substantially non-aqueous as used in this context means that while very small amounts of water may be incorporated into such preferred compositions as an impurity in the essential or optional components, the amount of water in non-aqueous liquid detergent compositions of the invention should in no event exceed about 5% by weight of the composition. More preferably, water content of the non-aqueous detergent composition will comprise less than about 1 % by weight.
  • the detergent composition of the invention comprises one or more surfactants, which may be non-ionic including semi-polar and/or anionic and/or cationic and/or zwitterionic.
  • the amount of the surfactant mixture component of the detergent compositions herein can vary depending upon the nature and amount of other composition components and depending upon the desired rheological properties of the ultimately formed composition. Generally, this surfactant mixture will be used in an amount comprising from about 0,1% to 90% by weight of the composition. More preferably, the surfactant mixture will comprise from about 10% to 60% by weight of the composition.
  • 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.
  • anionic surfactants are the linear alkyl benzene sulfonate (LAS) materials. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383, incorporated herein by reference.
  • sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the aikyi group is from about 11 to 14.
  • Sodium C 11 -C 14 e.g., C 12
  • LAS is especially preferred.
  • Other useful anionic surfactants are described in WO 99/0478, pages 11 through 13, incorporated herein by reference.
  • 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, alkyldimethylamineoxide, 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 also contain ampholytic and/or zwitterionic surfactants.
  • the hereinbefore described surfactant may be combined with a nonaqueous liquid diluent such as a liquid alcohol alkoxylate material or a nonaqueous, low-polarity organic solvent such as described in WO 99/0478, pages 14 through 17, incorporated herein by reference.
  • a nonaqueous, low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., Enzymes and/or bleach and/or activators, used in the liquid detergent compositions herein.
  • Such a solvent component will generally be utilized in an amount of from about 1% to 60% by weight of the composition. More preferably, the non-aqueous, low-polarity organic solvent will comprise from about 5% to 40% by weight of the composition, most preferably from about 10% to 25% by weight of the composition.
  • compositions of the invention may contain from about 0.01 % to about 10%, preferably from about 0.05% to about 2%, of ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine-N, N'-disuccinic acid
  • Preferred EDDS compounds for liquid detergent compositions are the free acid form and sodium sodium or potassium salts thereof. EDDS are described in US patent 4,704,233.
  • EDDS improves the efficiency of enzymes, especially amylases, in liquid non-aqueous detergent compositions upon dilution in the wash liquor.
  • ethylenediamine-N, N'-disuccinic acid or its salts act to bind heavy metal ions thereby preventing that heavy metal ions bind at the active site of the enzyme.
  • the binding of heavy metal ions at the active site of the enzyme results in generation of OH free radicals within the enzyme, resulting in destruction of the enzyme.
  • the liquid detergent compositions according to the present invention may also contain 0-65 % w/w other chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents, diphosphate, triphosphate, carbonate, citrate, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst) and mixtures thereof.
  • Further chelating agents are described in WO 99/00478 incorporated herein by reference.
  • the enzyme(s) in the particles of the invention may be also be stabilized conventionally using stabilizing agents in the liquid phase, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an 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.
  • stabilizing agents in the liquid phase e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an 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.
  • any enzyme in particular the enzyme of the invention, may be added in an amount corresponding to 0.01-100 mg of enzyme protein per liter of wash liquor, preferably 0.05-5 mg of enzyme protein per liter of wash liquor, in particular 0.1-1 mg of enzyme protein per liter 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.
  • Particulate material other than enzyme particles are Particulate material other than enzyme particles
  • the liquid detergent compositions of the invention may besides from the enzyme particles of the invention further comprise a Solid phase of particulate material which is dispersed and suspended within the liquid phase.
  • particulate material will range in size from about 0.1 to 1500 ⁇ m. More preferably such material will range in size from about 5 to 500 ⁇ m.
  • the particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the liquid phase of the composition.
  • the types of particulate materials which can be utilized may be selected from the following non-limiting list of useful components
  • the detergent may also contain other optional detergent ingredients.
  • the optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in the form of fine particles or droplets.
  • the types of materials which can be utilized may be selected from the following non-limiting list of useful components:
  • liquid detergent compositions herein can be prepared by mixing the liquid phase and by thereafter adding to this phase the additional particulate components in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a stable composition.
  • essential and certain preferred optional components will be combined in a particular order and under certain conditions.
  • Methods for preparing liquid detergents, including non-aqueous liquid detergents are well known to the art and an example may be found in WO 99/00478 pages 27-32, incorporated herein by reference.
  • the invention also relates to the use of a liquid composition of the invention for cleaning an item.
  • the item is preferably a cellulose containing fabric.
  • Preparation cf enzyme particles comprising spray dried protease enzyme in a NAFOL 1822 wax:
  • a non-aqueous liquid detergent comprising enzyme containing particles is prepared according to example 1, page 31-35 in WO 99/00471 except for replacing the "enzyme prills" of WO 99/00471 with the particles of example 1 or 2 or 3, supra.
  • a non-aqueous liquid detergent matrix was prepared according to guidelines given in patent application WO 99/00478 example 1, not adding the dry substances:

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Claims (65)

  1. Une composition détergente liquide essentiellement non aqueuse comprenant un tensioactif et dispersée dans la phase liquide des particules solides, dans laquelle les particules solides comportent une matrice de cire solide dans laquelle est réparti un agent actif, de préférence sous la forme de particules solides, lesquelles particules présentent une densité réelle comprise entre environ plus 0,5 g/cm3 et environ moins 0,5 g/cm3 de la densité réelle de la phase liquide et dans laquelle la cire est soluble dans l'eau ou dispersible dans l'eau.
  2. La composition liquide selon la revendication 1, dans laquelle la cire présente une densité réelle comprise entre environ plus 0,5 g/cm3 et environ moins 0,5 g/cm3 de la densité réelle de la phase liquide.
  3. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle la cire est insoluble ou non dispersible dans un liquide essentiellement non aqueux.
  4. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle la cire présente un point de fusion ou une gamme de fusion comprise entre environ 35° C et environ 120° C.
  5. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle la cire est choisie dans le groupe comprenant les polyéthylène glycols, les polypropylènes, les polyéthylènes, les cires tensioactives non ioniques, l'oxyde d'éthylène, l'oxyde de propylène ou leurs copolyméres, la cire de Carnauba, la cire de Candelilla, la cire d'abeille, le suif de boeuf hydrogénée, l'huile de palme hydrogénée, les graines de coton hydrogéné, l'huile de soja hydrogénée, les alcools d'acides gras, les monoglycérides, les diglycérides, les acides gras et les paraffines.
  6. La composition liquide selon la revendication 5, dans laquelle le polyéthylène glycol est choisi dans le groupe comprenant le PEG 1500, le PEG 3000, le PEG 4000, le PEG 6000 et le PEG 9000.
  7. La composition liquide selon la revendication 5, dans laquelle le tensioactif non ionique est un alcool gras éthoxylé.
  8. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle la matrice de cire solide comprend un mélange d'au moins deux cires.
  9. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle la quantité de cire est d'au moins 35 % p/p d'une particule renfermant une enzyme non enrobée.
  10. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle un modificateur de densité est réparti dans la matrice de cire.
  11. La composition liquide selon la revendication 10, dans laquelle ledit modificateur de densité présente une densité réelle qui est inférieure à 0,2 g/cm3 en dessous de la densité réelle de la matrice de cire solide comprenant l'enzyme.
  12. La composition liquide selon la revendication 11, dans laquelle ledit modificateur de densité est choisi dans le groupe comprenant les polysaccharides, les sphères légères et les gaz.
  13. La composition liquide selon la revendication 12, dans laquelle le gaz est l'air atmosphérique.
  14. La composition liquide selon la revendication 13, dans laquelle l'air est présent dans la particule sous la forme de bulles d'air réparties dans la matrice de cire solide.
  15. La composition liquide selon la revendication 12, dans laquelle la sphère légère est choisie parmi des particules sphériques creuses solides et des matériaux solides expansés.
  16. La composition liquide selon la revendication 15, dans laquelle le matériau solide expansé est du polystyrène.
  17. La composition liquide selon la revendication 15, dans laquelle les particules sphériques creuses solides sont constituées de verre, de céramique et de matière plastique.
  18. La composition liquide selon la revendication 12, dans laquelle le modificateur de densité est choisi parmi les gaz et les sphères légères et représente moins de 5 % p/p de la particule.
  19. La composition liquide selon la revendication 10, dans laquelle le modificateur de densité présente une densité réelle qui est moins de 0,2 g/cm3 au-dessus de la densité réelle de la matrice de cire solide comprenant l'enzyme.
  20. La composition liquide selon la revendication 19, dans laquelle le modificateur de densité est choisi dans le groupe comprenant les sels non organiques solubles ou insolubles dans l'eau, les argiles, les bentonites, les talcs, les zéolites et les silicates.
  21. La composition liquide selon la revendication 20, dans laquelle le sel non organique est un sulfate alcalin.
  22. La composition liquide selon la revendication 20, dans laquelle l'argile est le kaolin.
  23. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle la particule comprend, en outre, un ou plusieurs composés choisis parmi les stabilisants ou les agents protecteurs, les matériaux à fibre, les activateurs ou les cofacteurs, les dispersants, les agents de viscosité, les charges et les pigments.
  24. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle les particules comportent, en outre, une ou plusieurs couches d'enrobage entourant la matrice de cire.
  25. La composition liquide selon la revendication 24, dans laquelle l'enrobage comprend une cire.
  26. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle l'agent actif est une enzyme.
  27. La composition liquide selon l'une quelconque des revendications précédentes, dans laquelle l'enzyme est choisie dans le groupe comprenant les oxydoréductases (EC 1.-.-.-), les transférases (EC 2.-.-.-), les hydrolases (EC 3.-.-.-), les lyases (EC 4.-.-.-), les isomérases (EC 5.-.-.-) et les ligases (EC 6.-.-.-).
  28. La composition liquide selon la revendication 27, dans laquelle l'oxydoréductase est choisie dans le groupe comprenant les peroxydases (EC 1.11.1), les laccases (EC 1.10.3.2) et les glucose oxydases (EC 1.1.3.4).
  29. La composition liquide selon la revendication 27, dans laquelle l'hydrolase est choisie dans le groupe comprenant la cellulase, l'amylase, la protéase, la lipase et la mannanase.
  30. La composition détergente liquide selon la revendication 27, comprenant, en outre, un ou plusieurs composants choisis parmi les diluants liquides non aqueux, EDDS, les agents de chélation, les stabilisants d'enzymes, les agents de blanchiment, les activateurs de blanchiment, les adjuvants et les composés sources d'alcalinité.
  31. Procédé de préparation d'une composition détergente liquide essentiellement non aqueuse selon la revendication 1, comprenant l'étape de disperser les particules solides dans une phase liquide, dans lequel les particules comportent une matrice de cire solide dans laquelle est réparti un agent actif et ont une densité réelle comprise entre environ plus 0,5 g/cm3 et environ moins 0,5 g/cm3 de la densité réelle de la phase liquide et dans lequel la cire est soluble dans l'eau ou dispersible dans l'eau.
  32. Une particule renfermant une enzyme comprenant une matrice de cire solide d'un mélange d'au moins deux cires solides solubles dans l'eau, dans laquelle est réparti un agent actif, de préférence sous une forme particulaire solide.
  33. Une particule renfermant une enzyme comprenant une matrice de cire solide, dans laquelle sont répartis un agent actif, de préférence sous une forme particulaire solide, et un modificateur de densité et dans laquelle la cire est soluble dans l'eau ou dispersible dans l'eau.
  34. La particule renfermant une enzyme selon les revendications 32-33, dans laquelle la cire est insoluble ou non dispersible dans un liquide essentiellement non aqueux.
  35. La particule renfermant une enzyme selon les revendications 32-34, dans laquelle la cire présente un point de fusion ou une gamme de fusion comprise entre environ 35° C et environ 120° C.
  36. La particule selon les revendications 32-35, dans laquelle la quantité de cire est d'au moins 35 % p/p de la particule.
  37. La particule selon la revendication 33, dans laquelle la cire est choisie dans le groupe comprenant les polyéthylène glycols, les polypropylènes, les polyéthylènes, les cires tensioactives non ioniques, l'oxyde d'éthylène, l'oxyde de propylène ou leurs copolymères, la cire de Carnauba, la cire de Candelilla, la cire d'abeille, le suif de boeuf hydrogéné, l'huile de palme hydrogénée, les graines de coton hydrogéné, l'huile de soja hydrogénée, les alcools d'acides gras, les monoglycérides, les diglycérides, les acides gras et les paraffines.
  38. La particule selon les revendications 32-37, dans laquelle la cire est du polyéthylène glycol choisi dans le groupe comprenant le PEG 1500, le PEG 3000, le PEG 4000, le PEG 6000 et le PEG 9000.
  39. La particule selon les revendications 32-37, dans laquelle la cire est un tensioactif non ionique choisi parmi les alcools gras éthoxylés.
  40. La particule selon la revendication 32, comprenant, en outre, un modificateur de densité.
  41. La particule selon la revendication 33 ou 40, dans laquelle le modificateur de densité a une densité réelle qui est au moins 0,2 g/cm3 en dessous de la densité réelle de la matrice de cire solide comprenant l'enzyme.
  42. La particule selon la revendication 41, dans laquelle le modificateur de densité est choisi dans le groupe comprenant les polysaccharides, les sphères légères et les gaz.
  43. La particule selon la revendication 42, dans laquelle le gaz est l'air atmosphérique.
  44. La particule selon la revendication 43, dans laquelle l'air est présent dans la particule sous la forme de bulles d'air réparties dans la matrice de cire solide.
  45. La particule selon la revendication 42, dans laquelle la sphère légère est choisie parmi les particules sphériques creuses solides et les matériaux solides expansés.
  46. La particule selon la revendication 45, dans laquelle le matériau solide expansé est du polystyrène.
  47. La particule selon la revendication 45, dans laquelle les particules sphériques creuses solides sont constituées de verre, de céramique et de matière plastique.
  48. La particule selon la revendication 42, dans laquelle le modificateur de densité est choisi parmi les gaz et les sphères légères et représente moins de 5 % p/p de la particule.
  49. La particule selon la revendication 33 ou 40, dans laquelle le modificateur de densité a une densité réelle qui est au moins 0,2 g/cm3 au-dessus de la densité réelle de la matrice de cire solide comprenant l'enzyme.
  50. La particule selon la revendication 49, dans laquelle le modificateur de densité est choisi dans le groupe comprenant les sels non organiques solubles dans l'eau ou les sels non organiques insolubles dans l'eau, les argiles, les bentonites, les talcs, les zéolites et les silicates.
  51. La particule selon la revendication 50, dans laquelle le sel non organique est du sulfate alcalin.
  52. La particule selon la revendication 50, dans laquelle l'argile est le kaolin.
  53. La particule selon les revendications 32-52, dans laquelle la matrice de cire comprend, en outre, répartis dans celle-ci un ou plusieurs composés choisis parmi les agents stabilisants ou les protecteurs, les matériaux en fibre, les activateurs ou les cofacteurs, les dispersants, les agents de viscosité, les charges et les pigments.
  54. La particule selon les revendications 32-53, dans laquelle l'agent actif est une enzyme.
  55. La particule selon la revendication 54, dans laquelle l'enzyme est choisie dans le groupe comprenant les oxydoréductases (EC 1.-..-), les transférases (EC 2.-.. -), les hydrolases (EC 3.-..-), les lyases (EC 4.-.-.-), les isomérases (EC 5.-.-.-) et les ligases (EC 6.-..-).
  56. La particule selon la revendication 55, dans laquelle l'oxydoréductase est choisie dans le groupe comprenant les peroxydases (EC 1.11.1), les laccases (EC 1.10.3.2) et les glucose oxydases (EC 1.1.3.4).
  57. La particule selon la revendication 55, dans laquelle l'hydrolase est choisie dans le groupe comprenant la cellulase, l'amylase, la protéase, la lipase et la mannanase.
  58. La particule selon les revendications 32-57, dans laquelle la particule comprend, en outre, une ou plusieurs couches d'enrobage entourant la matrice de cire.
  59. La particule selon la revendication 58, dans laquelle l'enrobage comprend une cire.
  60. Un procédé pour préparer une particule comprenant un agent actif réparti dans une matrice de cire soluble dans l'eau ou dispersible dans l'eau, comprenant les étapes de :
    (a) préparer un mélange I comprenant une première cire, de préférence sous une forme fondue et un modificateur de densité, ou
    (b) préparer un mélange II comprenant une première cire, de préférence sous une forme fondue, et une ou plusieurs cires supplémentaires, de préférence sous une forme fondue, ayant une densité réelle inférieure ou supérieure à la première cire et un modificateur de densité,
    (c) disperser ou dissoudre un agent actif dans les mélanges I ou II,
    (d) préparer des particules renfermant un agent actif en solidifiant la dispersion ou la solution obtenue dans l'étape (c).
  61. Le procédé selon la revendication 60, comprenant l'étape (a).
  62. Le procédé selon la revendication 60, comprenant l'étape (b).
  63. Le procédé selon la revendication 60, comprenant l'étape (d) comprenant les étapes de :
    (a) atomiser la dispersion ou solution selon des gouttelettes et
    (b) solidifier les gouttelettes selon des particules solides en refroidissant les gouttelettes.
  64. Utilisation du détergent liquide selon les revendications 1-30 pour le nettoyage d'un article.
  65. L'utilisation selon la revendication 64, dans laquelle l'article est un tissu renfermant de la cellulose.
EP00960378A 1999-09-24 2000-09-22 Particules pour compositions liquides Expired - Lifetime EP1220885B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK135899 1999-09-24
DKPA199901358 1999-09-24
PCT/DK2000/000524 WO2001023513A1 (fr) 1999-09-24 2000-09-22 Particules pour compositions liquides

Publications (2)

Publication Number Publication Date
EP1220885A1 EP1220885A1 (fr) 2002-07-10
EP1220885B1 true EP1220885B1 (fr) 2006-05-17

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EP00960378A Expired - Lifetime EP1220885B1 (fr) 1999-09-24 2000-09-22 Particules pour compositions liquides

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EP (1) EP1220885B1 (fr)
CN (1) CN1378590B (fr)
AT (1) ATE326520T1 (fr)
AU (1) AU7271300A (fr)
DE (1) DE60028063T2 (fr)
WO (1) WO2001023513A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4559227B2 (ja) 2002-10-09 2010-10-06 ノボザイムス アクティーゼルスカブ 粒子組成物を改良する方法
DE602004021242D1 (de) * 2003-03-18 2009-07-09 Novozymes As Umhüllte enzymkörnchen
DE102004047097A1 (de) * 2004-09-29 2006-04-06 Henkel Kgaa Wasch- und Reinigungsmittel mit immobilisierten aktiven Inhaltsstoffen
DE102006055669A1 (de) 2006-11-23 2008-07-17 Henkel Kgaa Enzymzubereitung mit trägergebundenen Antioxidationsmitteln
US20090209447A1 (en) * 2008-02-15 2009-08-20 Michelle Meek Cleaning compositions
MX2011004066A (es) † 2008-11-03 2011-05-19 Danisco Inc Sistema de suministro para enzimas y sustratos co-formulados.
NO2719169T3 (fr) * 2014-06-17 2018-06-23
JP2020527339A (ja) * 2017-06-30 2020-09-10 ダニスコ・ユーエス・インク 低凝集の酵素含有粒子
WO2019125683A1 (fr) * 2017-12-21 2019-06-27 Danisco Us Inc Granulés thermofusibles contenant des enzymes, comprenant un déshydratant thermotolérant

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919841A (en) * 1988-06-06 1990-04-24 Lever Brothers Company Wax encapsulated actives and emulsion process for their production
GB8902909D0 (en) * 1989-02-09 1989-03-30 Unilever Plc Coating process
US5258132A (en) * 1989-11-15 1993-11-02 Lever Brothers Company, Division Of Conopco, Inc. Wax-encapsulated particles
ES2071418T3 (es) * 1991-04-24 1995-06-16 Unilever Nv Particulas encapsuladas con cera y procedimiento de fabricacion de las mismas.
JP2002512654A (ja) * 1997-06-27 2002-04-23 ザ、プロクター、エンド、ギャンブル、カンパニー 低密度酵素粒子を含む非水性液体洗剤組成物

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Publication number Publication date
CN1378590B (zh) 2010-05-12
AU7271300A (en) 2001-04-30
ATE326520T1 (de) 2006-06-15
WO2001023513A1 (fr) 2001-04-05
DE60028063T2 (de) 2006-12-21
EP1220885A1 (fr) 2002-07-10
CN1378590A (zh) 2002-11-06
DE60028063D1 (de) 2006-06-22

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