DE60028063T2 - PARTICLES FOR LIQUID PREPARATIONS - Google Patents

Abstract

The invention relates to a liquid composition comprising dispersed herein solid particles comprising a solid wax matrix, wherein an active is distributed. The invention also relates to particles in the liquid composition and the processes and uses of the composition and the particles.

Description

AREA OF EXPERTISE

These The invention relates to a drug-containing particle having a structure, which it is for insertion in liquid Makes compositions suitable. Furthermore, the invention relates Process for the preparation of active ingredient-containing particles and liquid compositions, like liquid Detergents comprising the active ingredient-containing particle. The invention also relates to the use of the active ingredient-containing particles and liquid Compositions comprising the active ingredient-containing particle.

BACKGROUND

Detergent products in the form of a liquid are often considered cheaper to use considered as dry powdery or particulate Detergent products. These detergents are therefore available to consumers considerable Found appeal. Such detergent products are easy to measure, quickly dissolve in the wash water, in concentrated solutions or dispersions on soiled areas of garments that to be washed, easy to apply and are not dusting. she usually occupy also less storage space than granulate products. In addition, such Containing detergents in their formulations, the drying processes without damage not survive could the operations often in the preparation of particulate or granular detergent products be used.

Even though such detergents have a number of advantages over granular detergent products, they also have several disadvantages. In particular interaction or react detergent composition ingredients present in granule products incompatible with each other tend to be together. Consequently, ingredients such as enzymes or other agents while maintaining an acceptable level of stability of the enzymes possibly especially difficult in liquid To introduce detergent products.

firm enzyme-containing particles and their use in dry powder detergents are known in the art from various disclosures. See for example: Michael S. Showell (editor); Powdered detergents; Surfactant Science Series; 1998; Vol. 71; Page 140-142; Marcel Dekker.

However, the use of solid composite particles comprising agents such as enzymes in liquid compositions such as detergents is an area that has not been thoroughly explored. Only a few disclosures relevant to this field have been found, such as WO 96/10073, which discloses "Nonaqueous Bleach-containing liquid detergent compositions"; WO 97/00938, "Nonaqueous, particulate-containing liquid detergent compositions with alkyl benzene sulfonate surfactant "disclosed; WO 99/00471, which discloses "non-aqueous liquid detergent compositions having reduced-density particles", and WO 99/99/00478, which discloses "non-aqueous liquid detergent compositions containing enzyme particles". Also for the present invention are the disclosures US 4,016,040 ; US 4,713,245 ; US 5,198,353 ; US 5,324,445 ; 5,492,646 prior art. Furthermore, active ingredients, such as bleach introduced into wax capsules, are made EP 346 034 known.

DESCRIPTION THE DRAWINGS

1 shows a diagram for a method for the preparation of enzyme-containing particles of the invention. A = molten wax comprising enzyme, B = atomizer, C = cooling air inlet, D = air outlet; F = cooler; G = sieves; H = finished enzyme-containing particles; I = particles of exceptional size for recycling.

SUMMARY THE INVENTION

It is an object of the invention to provide liquid compositions comprising an active agent wherein the active ingredient is protected from being inactivated by other ingredients of the composition or wherein the active ingredient is prevented from inactivating other components of the composition. We have found this to be achieved by incorporating the active ingredient into solid particles which may be dispersed in liquid compositions. For the application of such dispersions, it is important to be able to concentrate, agglomerate or otherwise formulate mechanisms that concentrate the particles in specific parts or layers of the liquid particle-introducing composition to prevent. Accordingly, it is a further object of the invention to provide particles which can be dispersed in a liquid composition, thereby improving the dispersion stability. A still further object of the invention is to provide a good process for preparing particles suitable for incorporation of an active ingredient and in which the properties of the resulting particles can be readily adjusted to suit the properties of the liquid into which the Particles are to be dispersed, adjust so as to improve the dispersion stability of the particles in the liquid composition.

We found that particles comprising a solid wax matrix in which an active substance, preferably in solid particle form, is distributed, an excellent solution for the Objects of the invention provides. Accordingly, the invention relates liquid Compositions dispersed in a liquid phase solid particles, wherein the solid particles are a solid wax matrix in which an active ingredient, preferably in solid particulate form, is distributed.

The The invention also relates to a particle comprising a solid matrix a mixture of at least two solid waxes, in which an active ingredient, preferably in solid particulate form, is distributed.

The The invention further relates to a particle comprising a solid Matrix in which an active ingredient, preferably in solid particle form, and a density modifier are distributed.

Yet Furthermore, the invention relates to processes for the preparation of liquid compositions of the invention and methods of making particles of the invention and the use of liquid Compositions and particles of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention offers several advantages: It is possible to use particles with a narrow size distribution and a very even actual Density of the particles produce. A narrow size distribution of enzyme-containing Particles were conventional he wishes, because the actual Density of known particles varies with the size of the particles. however becomes more uniform the actual density the particle size distribution less important, to the extent that in which the differences in the actual density between smaller ones and larger particles lose weight. By the method for producing the particles of the invention can the actual Density of the particles can be adjusted so that they match the density the liquid, in which the particles are to be dispersed, resulting in dispersions of particles in the liquid be enabled with an improved dispersion stability. Furthermore may be the chemical and / or physical stability of the active ingredient by introducing the active ingredient into a solid wax matrix by adding the active ingredient to a liquid composition without Incorporation into the particles of the invention can be improved.

Yet can continue any risks such as dust formation, toxicity and the like in which Handling the active ingredient before forming a liquid dispersion, e.g. if the active ingredient is in pure dry form, through Lowering the drug into a wax matrix lowered and further by coating the particle with an active substance-free coating layer be improved.

definitions

The term "actual density" of a compound, as used herein, refers to the density, by weight, per volume of the compound obtained by immersing a weighed amount of the compound in a liquid in which the compound is insoluble, and measuring the volume increase of the liquid dispersion (ie the volume of liquid which is displaced by the compound) is determined. for example, if 1 gram of a compound of a volume of 10 cm ³ of a liquid is added, in which the compound is insoluble, and, through the addition of the volume of the liquid-connection To 11 cm ³ , with the compound thereby displacing 1 cm ^{3 of} liquid, the actual density of the compound is 1 gram per cm ^3. The actual density of a liquid can be measured as the weight of a measured volume of the liquid.

Of the Term "wax" applies as used herein for one Compound with a melting point between 25-150 ° C.

The term "solid wax matrix" as used herein applies as wax in a solid particulate Phase in which enzymes and other beneficial ingredients are dispersed, and wherein the wax is used to set and / or bind the other ingredients together to form a solid separate and particulate unit. In an uncoated particle, the wax or wax mixture forming the wax matrix constitutes at least 35% by weight of the particle in which the active ingredient and other beneficial ingredients are distributed.

Of the Term "distributed" should, as here in Reference to agents distributed in a wax matrix uses such Understand that the active ingredient is uniform or homogeneous throughout Wax matrix, e.g. as active ingredient dissolved in the wax and / or as Separate drug clusters or particles homogeneously dispersed in the wax are present.

The particle

The active agent-containing particle provided by the invention comprises a solid wax matrix and an active agent, preferably in solid particulate form, and optionally other useful ingredients other than the wax and the active agent dispersed in the solid wax matrix, and optionally the particle coated one or more coating layers. The particulate components which include the coating materials are preferably dispersible or soluble at neutral to alkaline pH in aqueous solutions containing more than 50% by weight of water. Useful particle sizes are in the range of about 20 to about 2000 microns, preferably between about 100 to about 1000 microns, for example between about 200 to about 600 microns. The actual density of the particles is between about plus 0.5 g / cm ³ to about minus 0.5 g / cm ^{3 of} the actual density of the liquid phase in which the particles are to be dispersed. This means that if the liquid phase has an actual density of, for example, 2 g / cm ³ , the actual density of the particles should be between about 1.5 g / cm ³ to about 2.5 g / cm ³ . Preferably course smaller difference between the true densities of the particles and the liquid phase are better, so is the actual density of the particles is between about plus 0.3 g / cm ³ to about minus 0.3 g / cm ^3, for example between about 0, 1 g / cm ³ to about minus 0.1 g / cm ^{3 of} the actual density of the liquid phase. For small particles, eg for sizes between 50 to 200 μm, the difference in actual density between the particles and the liquid phase may be greater depending on the viscosity of the liquid phase. For such small particles, the actual density of the particles may be outside the range of the actual density of the liquid plus or minus 0.5 g / cm ³ . In this embodiment of the invention, particles having a size such as between 50 to 200 μm may have an actual density, for example in the ranges plus or minus 0.5-1.5 g / cm ^{3 of} the actual density of the liquid phase.

wax matrices

As As described above, the particles of the invention comprise in one Aspect of the invention a solid wax matrix in which an active ingredient is distributed. As defined above, a wax is a compound that has a melting point between 20-150 ° C. Preferred waxes are organic compounds or salts of organic Compounds with a melting point in this range. We found surprising that it is possible is, using a wax matrix as a carrier for the active ingredient, drug particles to produce for which the actual Density can be easily adjusted and controlled. Also found us that it is possible using a wax matrix Particles of highly controllable and uniform size with a fairly narrow particle size Particle distribution to obtain (see below the methods relating to Section).

The solid wax matrix may be any wax or wax mixture, that for the purpose of introducing the finished particle into a liquid composition suitable is. In the context of the invention, the term "wax" as used herein includes also mixtures of two or more different waxes. mixtures of different waxes, optionally in combination with heavy ones and / or light solids, are preferred because by mixing of waxes with different properties and optional mixtures of heavy and light particles with a desired particle actual Density can be obtained. Accordingly, the invention provides a particle which is a mixture comprising at least two waxes. Also included in the Invention are enzyme particles which are a mixture of 3, 4 or even 5 waxes include.

Also, an important feature of the wax or wax mixture is that the wax should preferably be water-soluble or water-dispersible in neutral and alkaline solution, such that when the liquid composition of the invention is incorporated into an aqueous solution, ie by diluting with water, the burst solid wax matrix of the particles and / or should dissolve to a to provide rapid release and dissolution of the drug introduced into the particles into the aqueous solution. Examples of water-soluble waxes are polyethylene glycols (PEGs). Accordingly, the solubility of the wax among the water-soluble waxes in water should preferably be up to 75 parts wax per 25 parts water, as for PEG 1000. Among water-insoluble waxes which are dispersible in an aqueous solution are triglycerides and oils.

Of Solve further yourself or blow up useful Do not wax in a substantially non-aqueous liquid phase. Of the Term "im Essentially non-aqueous "may be in this context as the liquid phase which are low (for example less than 5% by weight or less than 3% by weight) or no water (non-aqueous). Water, if that in the non-aqueous solution The invention is preferably due to the inclusion of hydrogenated compounds. The wax should also be with the active ingredient compatible be, i. it should be the active ingredient e.g. by reacting with the Active ingredient or permanent modification of structures, as in the case of polypeptides, folds, helical ones Parts, sheet-shaped Parts, prosthetic groups, and the like that are needed that the active substance has the activity maintains, do not inactivate. Even further, the wax should contain the active ingredient be miscible, i. The active ingredient may be in the (molten) wax solve and / or the active ingredient may be in dry (particulate) wax in 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 has a melting point or melting range (polymer waxes tend to melt over a temperature range) 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 in producing particles are considered when the melting point of the wax is below 35 ° C. The upper temperature limit is set as the maximum temperature usually applicable to drugs without significant loss of activity due to, for example, 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. In a specific embodiment the true density of the wax is 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 , eg between about 0.1 g / cm ³ to about minus 0.1 g / cm ³ . The actual density of the wax or wax mixture itself is preferably lower than 1.4 g / cm ³ , more preferably lower than 1.2 g / cm ³ , even more preferably lower than 1.1 g / cm ³ . However, as described above, the actual density of the finished particle is important, and thus the actual density of the wax may be significantly higher or lower than the liquid phase when the particles are small, such as between 50-200 μm, or other ingredients. which may be included in the particle, compensate to adjust the actual density of the particles.

In a further preferred embodiment For example, the wax of the invention has a molecular weight between about 150 daltons to about 10,000 daltons.

• – Wachs vom Polyethylenglycol-Typ, abgekürzt PEG. Verschiedene PEG-Wachse sind mit unterschiedlichen Molekulargrößen im Handel erhältlich, wobei PEGs mit niedrigen Molekulargrößen auch die niedrigsten Schmelzpunkte aufweisen. Beispiele für geeignete PEGS sind PEG 1500, PEG 3000, PEG 4000, PEG 6000, PEG 9000, z.B. von BASF – Deutschland. Um den gewünschten Eigenschaften der tatsächlichen Dichte und des Schmelzpunkts für das Wachs und/oder die Enzymteilchen zu genügen, wird auch erwogen, dass Gemische aus Wachsen mit niedrigem Schmelzpunkt mit Wachsen mit hohem Schmelzpunkt eine sehr nützliche Ausführungsform der Erfindung sind.
• – Polypropylene oder Polyethylene oder Gemische davon.
• – Nicht-ionische Tenside, die bei Raumtemperatur fest sind, wie ethoxylierte Fettalkohole mit einem hohen Gehalt an Ethoxygruppen, wie Lutensol AT80 von BASF mit 80 Ethylenoxideinheiten pro Molekül. Alternativ dazu sind Polymere von Ethylenoxid, Propylenoxid oder Copolymere davon nützlich, wie in Blockpolymeren, z.B. Pluronic PE 6800 von BASF Deutschland.
• – Wachse, die von natürlichen Quellen isoliert sind, wie Carnaubawachs (Schmelzpunkt zwischen 80–88°C), Candelillawachs (Schmelzpunkt zwischen 68–70°C) und Bienenwachs. Andere natürliche Wachse oder Derivate davon sind Wachse, die von Tieren oder Pflanzen abgeleitet sind, z.B. maritimen Ursprungs. Beispiele für derartige Wachse sind hydrierter Rindertalg, hydriertes Palmöl, hydriertes Baumwollsamenöl und/oder hydriertes Sojabohnenöl, wobei der Begriff „hydriert", wie hier verwendet, als Sättigung von ungesättigten Kohlenhydratketten gilt, z.B. in Triglyceriden, wobei Kohlenstoff-Kohlenstoff-Doppelbindungen zu Kohlenstoff-Kohlenstoff-Einfachbindungen umgewandelt werden. Ein Beispiel für hydriertes Palmöl ist im Handel z.B. von Hobum Öle und Fette GmbH – Deutschland oder Deutsche Cargill GmbH – Deutschland – erhältlich.
• – Fettsäurealkohole, wie der lineare langkettige Fettsäurealkohol NAFOL 1822 (C_18,20,22) von Condea Chemie GmbH – Deutschland, mit einem Schmelzpunkt zwischen 55–60°C und einer tatsächlichen Dichte von etwa 0,96 g/cm³.
• – Monoglyceride und/oder Diglyceride, wie Glycerylstearat, wobei Stearat ein Gemisch aus Stearin- und Palmitinsäure ist, sind nützliche Wachse. Ein Beispiel dafür ist Dimodan PM – von Danisco Ingredients, Dänemark – mit einer tatsächlichen Dichte von etwa 1 g/cm³.
• – Fettsäuren, wie hydrierte lineare langkettige Fettsäuren.
• – Paraffine, d.h. feste Kohlenwasserstoffe.
• – Mikrokristallines Wachs.

The wax of the invention may be any wax that is chemically synthesized. It may as well be a wax isolated from a natural source or derivative thereof. Accordingly, the wax of the invention is preferably selected from the following non-limiting list of waxes.

• Polyethylene glycol type wax, abbreviated PEG. Various PEG waxes are commercially available with different molecular sizes, with low molecular weight PEGs also having the lowest melting points. Examples of suitable PEGS are PEG 1500, PEG 3000, PEG 4000, PEG 6000, PEG 9000, eg from BASF - Germany. In order to meet the desired properties of actual density and melting point for the wax and / or enzyme particles, it is also contemplated that mixtures of low melting waxes with high melting point waxes are a very useful embodiment of the invention.
• Polypropylene or polyethylenes or mixtures thereof.
• Nonionic surfactants which are solid at room temperature, such as ethoxylated fatty alcohols with a high content of ethoxy groups, such as Lutensol AT80 from BASF with 80 ethylene oxide units per molecule. Alternatively, polymers of ethylene oxide, propylene oxide or copolymers thereof are useful as in block polymers, eg Pluronic PE 6800 from BASF Germany.
• - Waxes isolated from natural sources, such as carnauba wax (melting point between 80-88 ° C), candelilla wax (melting point between 68-70 ° C) and beeswax. Other natural wake Se or derivatives thereof are waxes derived from animals or plants, eg maritime origin. Examples of such waxes are hydrogenated beef tallow, hydrogenated palm oil, hydrogenated cottonseed oil and / or hydrogenated soybean oil, where the term "hydrogenated" as used herein is considered to saturate unsaturated carbohydrate chains, eg, in triglycerides, where carbon-carbon double bonds are carbonated. An example of hydrogenated palm oil is commercially available from, for example, Hobum Oils and Fette GmbH - Germany or Deutsche Cargill GmbH - Germany.
• Fatty acid alcohols, such as the linear long-chain fatty acid alcohol NAFOL 1822 (C _{18, 20, 22} ) from Condea Chemie GmbH - Germany, having a melting point between 55-60 ° C. and an actual density of about 0.96 g / cm ³ .
• Monoglycerides and / or diglycerides, such as glyceryl stearate, where stearate is a mixture of stearic and palmitic acids, are useful waxes. An example of this is Dimodan PM - from Danisco Ingredients, Denmark - with an actual density of about 1 g / cm ³ .
• - fatty acids, such as hydrogenated linear long-chain fatty acids.
• Paraffins, ie solid hydrocarbons.
• - Microcrystalline wax.

In further embodiments are useful in the invention Waxes 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.

As as defined above the amount of wax in an uncoated enzyme-containing particle at least 35% by weight for the wax to form a solid matrix, as well as suitable pumping and atomization (see below). However, it is a preferred amount of wax is at least 50% by weight, such as at least 75% by weight.

drugs

Of the Active ingredient of the invention may be any active ingredient or a mixture of active ingredients which is therefrom Benefit that draws it from the liquid Phase of a liquid Composition is separated. The term "active ingredient" means that it contains all the ingredients includes, after release from the wax matrix by applying the composition or the particle of the invention in a method, a purpose of improving the method. Suitable active ingredients are those who experience either deactivation and / or one Reactivation of other ingredients in the compositions of Cause invention. As indicated, the active ingredient is preferably dispersed as separate solid particles in a solid wax matrix in front. Providing the active ingredient in solid form rather than dissolved in the wax, can more freedom to choose from different waxes and also one improved stability of the active ingredient.

Of the Active ingredient may be inorganic in nature, such as bleaching ingredients, such as mentioned below, or organic nature. Preferred active ingredients are biological effective materials, usually react very sensitively to the surrounding environment, such as materials, available from microorganisms are. Particularly preferred active substances are peptides or polypeptides, like enzymes.

The Enzyme in the context of the present invention may be any Enzyme or any combination of different enzymes that benefit from being brought into a particle are when they are in a liquid Detergent are included. Consequently, where reference is made to "an enzyme", This is generally understood to be combinations of one or more enzymes.

It should be understood that enzyme variants (made, for example, by recombinant techniques) are included within the meaning of the term "enzyme." Examples of such enzyme variants are described, for example, in US Pat EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV).

The Enzyme classification used in the present specification with the claims Follow the recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, Academic Press, Inc., 1992.

Accordingly, the types of enzymes suitably incorporated in the granules of the invention oxidoreductases (EC 1.-.-.-), transferases (EC 2.-.-.-), hydrolases (EC 3.-.-.-), lyases (EC 4.-.-.-) , Isomerases (EC 5.-.-.-), ligases (EC 6.-.-.-) and mannanases.

• a) Transferasen, die Gruppen mit einem Kohlenstoffatom transferieren (EC 2.1);
• b) Transferasen, die Aldehyd- oder Ketonreste transferieren (EC 2.2); Acyltransferasen (EC 2.3);
• c) Glycosyltransferasen (EC 2.4);
• d) Transferasen, die andere Alkyl- oder Arylgruppen als Methylgruppen transferieren (EC 2.5); und
• e) Transferasen, die stickstoffhaltige Gruppen transferieren (EC 2.6).

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 ^™ (enzyme available from Novo Nordisk A / S). Other oxidoreductases are available from other suppliers. Preferred transferases are transferases in any of the following subclasses:

• a) transferases that transfer groups with one carbon atom (EC 2.1);
• b) transferases that transfer aldehyde or ketone residues (EC 2.2); Acyltransferases (EC 2.3);
• c) glycosyltransferases (EC 2.4);
• d) transferases that transfer alkyl or aryl groups other than methyl groups (EC 2.5); and
• e) Transferases transferring nitrogen-containing groups (EC 2.6).

One Particularly preferred transferase is in the context of the invention a transglutaminase (protein glutamine-γ-glutamyltransferase, EC 2.3.2.13).

Further examples for suitable transglutaminases are described in WO 96/06931 (Novo Nordisk A / S) described.

preferred Hydrolases in the context of the invention are: carboxylic ester hydrolases (EC 3.1.1.-), such as lipases (EC 3.1.1.3); Phytases (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 into a group referred to herein as "carbohydrases"), such as α-amylases (EC 3.2.1.1); Peptidases (EC 3.4, also known as proteases); and other Carbonyl].

in the present context, the term "carbohydrase" is used to not only enzymes, the carbohydrate chains (e.g., starches or cellulose) in particular of five- or six-membered ring structures (i.e., glycosidases, EC 3.2) but also enzymes containing carbohydrates, e.g. six-membered ring structures, like D-glucose, to five-membered Ring structures, such as D-fructose, can beomerized.

carbohydrases close to relevance the following (EC numbers in parentheses): α-amylases (EC 3.2.1.1), β-amylases (EC 3.2.1.2), glucan-1,4-α-glucosidase (EC 3.2.1.3), Endo-1,4-beta-glucanase (cellulases, EC 3.2.1.4), endo-1,3 (4) -β-glucanases (EC 3.2.1.6), endo-1,4-β-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), β-glucosidases (EC 3.2.1.21), α-galactosidases (EC 3.2.1.22), β-galactosidases (EC 3.2.1.23), amylo-1,6-glucosidases (EC 3.2.1.33), xylan-1,4-β-xylosidases (EC 3.2.1.37), glucanendo-1,3-β-D-glucosidases (EC 3.2.1.39), α-dextrin-endo-1,6-α-glucosidases (EC3.2.1.41), sucrose-α-glucosidases (EC 3.2.1.48), glucanendo-1,3-α-glucosidases (EC 3.2.1.59), glucan-1,4-β-glucosidases (EC 3.2.1.74), glucanendo-1,6-β-glucosidases (EC 3.2.1.75), arabinanendo-1,5-α-L-arabinosidases (EC 3.2.1.99), lactases (EC 3.2.1.108), chitosanases (EC 3.2.1.132) and xylose isomerases (EC 5.3.1.5).

Examples of commercially available proteases (peptidases) include Kannase ^™ , Everlase ^™ , Esperase ^™ , Alcalase ^™ , Neutrase ^™ , Durazym ^™ , Savinase ^™ , Pyrase ^™ , pancreatic trypsin NOVO (PTN), Bio-Feed ^™ Pro and Clear-Lens ^™ Pro (all available from Novo Nordisk A / S, Bagsvaerd, Denmark).

Other commercially available proteases include Maxatase ^™ , Maxacal ^™ , Maxapem ^™ , Opticlean ^™ and Purafect ^™ (available from Genencor International Inc. or Gist-Brocades).

Examples of commercially available lipases include Lipoprime ^™ Lipolase ^™ , Lipolase ^™ Ultra, Lipozyme ^™ , Palatase ^™ , Novozym ^™ 435 and Lecitase ^™ (all available from Novo Nordisk A / S).

Other commercially available lipases include Lumafast ^™ (Pseudomonas mendocina lipase from Genencor International Inc.); Lipomax ^™ (Ps. Pseudoalcaligenes lipase from Gist-Brocades / Genencor Int. Inc.); and lipase from Bacillus sp. from Solvay Enzymes. Additional lipases are available from other suppliers.

Examples of commercially available carbohydrases include Alpha-Gal ^™ , Bio-Feed ^™ Alpha, Bio-Feed ^™ Beta, Bio-Feed ^™ Plus, Bio-Feed ^™ Plus, Novozyme ^™ 188, Celluclast ^™ , Cellusoft ^™ , Ceremyl ^™ , Citrozym ^TM , Denimax ^™ , Dezyme ^™ , Dextrozyme ^™ , Finizym ^™ , Fungamyl ^™ , Gamanase ^™ , Glucanex ^™ , Lacto zym ^™ , Maltogenase ^™ , Pentopan ^™ , Pectinex ^™ , Promozyme ^™ , Pulpzyme ^™ , Novamyl ^™ , Termamyl ^™ , AMG ^™ (Amyloglucosidase Novo), Maltogenase ^™ , Sweetzyme ^™ and Aquazym ^™ (all available from Novo Nordisk A / S) , Other carbohydrases are available from other suppliers.

Of the Enzyme content (calculated as pure enzyme protein) in a particle The invention typically ranges from about 0.05 to 50% by weight of the enzyme-containing particle.

Becomes for example, a protease (peptidase) in particles of the invention introduced, lies the enzyme activity (proteolytic activity) of the finished Granules typically in the range of 1-20 KNPU / g. This unit of protease activity is kilo Novo Protease Units (Kilo Novo Protease Units) per gram of sample (KNPU / g). The activity with respect to an enzyme standard of known activity in KNPU / g certainly. The enzyme standard is determined by measuring the rate of formation (Micromol / minute) at free amino groups by the digestion of Dimethylcasein (DMC) in solution released by the enzyme for a given amount of enzyme standardized. The rate of formation is determined by recording the linear absorption evolution at 420 nm of simultaneous Reaction between the formed free amino groups and added 2,4,6-tri-nitro-benzene sulfonic acid (TNBS) monitored. The digestion of DMC and the color reaction are at 50 ° C in a boric acid followed by a pH of 8.3 with a 9-minute reaction time from a 3-minute walk Measuring time, performed. A booklet AF 220/1 is available on request from Novo Nordisk A / S, Denmark, with the brochure here is incorporated by reference.

Equally is in the case of, for example, α-amylases an activity from 10-500 KNU / g typical. The activity with respect to an enzyme standard of known activity in KNU / g certainly. The enzyme standard is determined by measuring the rate of formation (Micromol / minute) of 2-chloro-4-nitrophenol by digestion of 2-chloro-4-nitrophenyl-b-D-maltoheptaoside substrate by the enzyme and alpha and beta-glucosidase accessory enzymes in solution is released for standardized a given amount of enzyme. Kits for performing α-amylase assays are commercially available. A description of an α-amylase assay is in leaflet AF318 / 1-GB on request from Novo Nordisk A / S, Denmark. For example is for lipases usually an activity in the range of 50-400 KLU / g suitable.

Other ingredients

The Particles of the invention can, as indicated, also contain one or more other ingredients, which differ from the active substance and the wax. These ingredients should preferably also in aqueous solution at neutral or alkaline pH dispersible or soluble be. The term "different" is in this context as an ingredient that is incompatible with either the active ingredient or the Wax is identical. Other ingredients may be incorporated into ingredients that contribute to Modifying the actual density of the particle (referred to herein as "density modifier"), and in constituents that impart different properties to the particle, be divided.

Density modifier

Density modifier are, as used here, as ingredients with a lower or higher actual Density defined as the wax matrix. The density modifier is preferably present as a solid or as a gas, dispersed in the Wax matrix, in front.

One preferred density modifier is a lightweight ingredient, to lower the actual Density of the particle of the invention is useful.

• – Leichte Kügelchen, die kleine Teilchen mit einer niedrigen tatsächlichen Dichte sind. Typischerweise sind sie hohle kugelförmige Teilchen mit Luft oder Gas in ihrem Inneren. Derartige Materialien werden gewöhnlich durch Ausdehnen eines festen Materials hergestellt. Diese leichten Kügelchen können anorganischer Natur sein, wie Scotchlite^TM Glass Bubbles von 3M^TM (hohle Glaskügelchen), Q-CEL^® (hohle Mikrokügelchen von Borsilikatglas) und/oder Extendospheres^® (keramische hohle Kügelchen), erhältlich von The PQ Corporation. Die leichten Kügelchen können auch organischer Natur sein, wie die PM-Serie (hohle Kunststoffkügelchen), erhältlich von The PQ Corporation. Expancel^® (hohle Kunststoffkügelchen) von AKZO Nobel, Luxsil^® und Sphericel^® von Potters Industries und/oder Styrocell^® von SHELL, bei welchen es sich um Kügelchen aus Polystyrol handelt. Das Polystyrol von Styrocell^® enthält Pentan, das bei Erwärmen kocht und sich ausdehnt oder das Material aufknallt (die Reaktion ist vergleichbar mit der Ausdehnung von Maiskörnern zu Popcorn), wodurch ein leichtes Polystyrolmaterial mit einer niedrigen tatsächlichen Dichte hinterlassen wird. Auch sind Polysaccharide, wie Stärke oder Derivate davon, bevorzugt. Biodac^® ist ein Beispiel für nicht hohles, leichtgewichtiges Material, das aus Zellulose (Abfall aus der Papierherstellung), erhältlich von GranTek Inc., hergestellt wird. Diese Materialien können in das Granulat der Erfindung entweder allein oder als Gemisch von verschiedenen leichten Materialien eingeschlossen sein. Gewöhnlich sind nur kleine Mengen an leichtem Material nötig, so dass ein nützlicher Gehalt an Gas im Enzymteilchen unter 10 Gew.-% des fertigen Teilchens, vorzugsweise unter 5 Gew.-%, stärker bevorzugt unter 3 Gew.-% liegt, z.B. etwa 0,1–1 Gew.-% beträgt.
• – Gase, wie Atmosphärenluft (bevorzugt) oder andere Gase, z.B. Stickstoff. Ein Gas kann in die Wachsmatrix während der Verfestigung des Wachses, z.B. in Form von kleinen Blasen, eingebracht und dort eingeschlossen werden, wodurch die tatsächliche Dichte des fertigen Enzymteilchens reduziert wird. Gewöhnlich ist nur wenig Gas nötig, so dass ein nützlicher Gasgehalt im Enzymteilchen unter 5 Gew.-% des fertigen Teilchens, vorzugsweise unter 3 Gew.-%, stärker bevorzugt unter 1 Gew.-% liegt, z.B. etwa 0,1 Gew.-% beträgt.

A light component has a lower actual density than the actual density of the solid wax matrix, thereby allowing adjustment of the actual density of the finished particle. In a specific embodiment, the actual density of the light component is at least 0.2 g / cm ³ lower than the actual density of the enzyme-incorporating solid wax matrix, preferably at least 0.4 g / cm ³ lower, eg, at least 0.6 g / cm ³ lower than the enzyme-introducing solid wax matrix. Lightweight components can be selected from the following non-limiting list:

• - Light spheres, which are small particles with a low actual density. Typically, they are hollow spherical particles with air or gas in their interior. Such materials are usually made by expanding a solid material. These lightweight beads can be of inorganic nature, such as Scotchlite ^™ Glass Bubbles from 3M ^™ (hollow glass spheres), Q-CEL ^® (hollow microspheres of borosilicate glass) and / or Extendospheres ^® (ceramic hollow spheres) available from The PQ Corporation. The lightweight beads may also be organic in nature, such as the PM series (hollow plastic beads) available from The PQ Corporation. Expancel ^® (hollow plastic spheres) from AKZO Nobel, Luxsil ^® and Sphericel ^® from Potters Industries and / or Styrocell ^® from Shell, in which it is spheres of polystyrene. The polystyrene of Styrocell ^® contains pentane which upon heating boils and expands or material aufknallt (the reaction is comparable to the expansion of corn seeds into popcorn) is left whereby a light polystyrene material of a low true density. Also, polysaccharides such as starch or derivatives thereof are preferred. Biodac ^® is an example of non-hollow lightweight material made from cellulose (waste from papermaking), available from GranTek Inc., is prepared. These materials may be included in the granules of the invention either alone or as a mixture of various lightweight materials. Usually, only small amounts of light material are needed so that a useful level of gas in the enzyme particle is below 10% by weight of the finished particle, preferably below 5% by weight, more preferably below 3% by weight, eg, about zero , 1-1 wt .-% is.
• - Gases, such as atmospheric air (preferred) or other gases, such as nitrogen. A gas may be introduced into the wax matrix during solidification of the wax, eg in the form of small bubbles, and entrapped therein, thereby reducing the actual density of the final enzyme particle. Usually, little gas is required so that a useful gas content in the enzyme particle is below 5% by weight of the finished particle, preferably below 3% by weight, more preferably below 1% by weight, eg, about 0.1% by weight. % is.

• – Wasserlösliche und/oder unlösliche anorganische Materialien, wie Salze, insbesondere Alkalisalze, z.B. sind fein zermahlenes Alkalisulfat (wasserfreies Na₂SO₄ weist eine tatsächliche Dichte von etwa 2,7 g/cm³ auf), Alkalicarbonat und/oder Alkalichlorid; Tone, wie Kaolin (z.B. Speswhite^TM, English China Clay); Bentonite; Talkum; Zeolithe und/oder Silicate nützlich.

In another preferred embodiment, the density modifier is a heavy component useful for adjusting the actual density of the particle of the invention. A heavy component has a higher actual density than the actual density of the enzyme-incorporating solid wax matrix, thereby enabling adjustment of the actual density of the final enzyme particle. In a specific embodiment, the actual density of the light material is at least 0.2 g / cm ³ higher than that of the enzyme-incorporating solid wax matrix, preferably at least 0.4 g / cm ³ higher, eg, at least 0.6 g / cm ³ higher than the enzyme-introducing solid wax matrix. Heavy material may be selected from the following non-limiting list:

• Water-soluble and / or insoluble inorganic materials, such as salts, in particular alkali metal salts, for example finely ground alkali metal sulfate (anhydrous Na ₂ SO ₄ has an actual density of about 2.7 g / cm ³ ), alkali metal carbonate and / or alkali metal chloride; Clays such as kaolin (eg Speswhite ^™ , English China Clay); bentonite; Talc; Zeolites and / or silicates useful.

Ingredients belonging to the Give particles different properties

• – Stabilisations- und/oder Schutzmittel. Stabilisations- oder Schutzmittel können in mehrere Kategorien fallen: alkalische oder neutrale Materialien, Reduktionsmittel, Antioxidationsmittel und/oder Salze von Ionen der ersten Übergangsmetallreihe. Jedes davon kann in Verbindung mit anderen Schutzmitteln derselben oder unterschiedlicher Kategorien verwendet werden. Beispiele für alkalische Schutzmittel sind Alkalimetallsilikate, -carbonate oder -bicarbonate, die eine chemische Radikalfängerwirkung durch aktives Neutralisieren bereitstellen, z.B. Oxidationsmittel. Beispiele für Reduktionschutzmittel sind Salze von Sulfit, Thiosulfit oder Thiosulfat, während Beispiele für Antioxidationsmittel Ascorbinsäure, Methionin, butyliertes Hydroxytoluol (BHT) oder butyliertes Hydroxyanisol (BHA) sind. Besonders bevorzugte Mittel sind Salze von Thiosulfaten, z.B. Natriumthiosulfat. Nützliche Enzymstabilisatoren, insbesondere für Proteaseenzyme, können Borate, Borax, Formiate, Di- und Tricarbon-säuren und umkehrbare Enzymhemmer, wie organische Verbindungen mit Sulfhydrylgruppen, oder alkylierte oder arylierte Borsäuren sein. Beispiele für Stabilisatoren auf Borbasis sind in WO 96/21716 zu finden, wohingegen es sich bei einem ein bevorzugten Stabilisator auf Borbasis um 4-Formylphenylborsäure oder Derivate davon, beschrieben in WO 96/41859, wobei beide Offenbarungen hier unter Bezugnahme eingebracht sind, handelt. Noch andere Beispiele für nützliche Enzymstabilisatoren sind Gelatine, Casein, Polyvinylpyrrolidon (PVP) und Pulver von entrahmter Milch.
• – Enzymaktivatoren und -cofaktoren, die im Waschverfahren zum Aktivieren oder Verbessern der Wirkung des Enzyms verwendet werden können. Verschiedene organische Verstärker oder Aktivatoren, die als Elektronendonoren für Oxidoreduktaseenzyme für verschiedene Zwecke, wie bleichende oder antimikrobielle Wirkung, wirken, sind auf dem Fachgebiet bekannt (z.B. aus WO 94/12620, WO 94/12621, WO 95/01626 und WO 96/00179) und können geeigneter Weise in das Enzymteilchen eingebracht werden. Bei einer Gruppe von bevorzugten organischen Verstärkern handelt es sich um Phenolverbindungen (Alkylsyringate) der Formel:
  
  wobei der Buchstabe A in der Formel eine Gruppe wie -D, -CH=CH-D, -CH=CH-CH=CH-D, -CH=N-D, -N=N-D oder -N=CH-D bezeichnet, wobei D ausgewählt ist aus der Gruppe, bestehend aus -CO-E, -SO₂-E, -N-XY und -N⁺-XYZ, wobei E -H, -OH, -R oder -OR sein kann und X und Y und Z identisch oder unterschiedlich und ausgewählt sein können aus -H und -R; wobei R ein C₁-C₁₆-Alkyl, vorzugsweise ein C₁-C₈-Alkyl ist, wobei dieses Alkyl gesättigt oder ungesättigt, verzweigt oder unverzweigt und wahlweise substituiert sein kann mit einer Carboxy-, Sulfo- oder Aminogruppe; und B und C gleich oder verschieden und ausgewählt sein können aus C_mH_2m+1, wobei m = 1, 2, 3, 4 oder 5 ist. In der vorstehend erwähnten Formel kann A in Metastellung zu der Hydroxygruppe statt in der wie dargestellten Parastellung angeordnet sein. In besonderen Ausführungsformen der Erfindung ist der Enzymaktivator oder -verstärker ausgewählt aus der Gruppe mit der Formel:
  
  in welcher A eine Gruppe wie -H, -OH, -CH₃, -OCH₃, -O(CH₂)_nCH₃ ist, wobei n = 1, 2, 3, 4, 5, 6, 7 oder 8 ist. Eine andere bevorzugte Gruppe von gut funktionierenden organischen Enzymaktivatoren oder -verstärkern umfasst eine -CO-NOH-Gruppe und weist die folgende Formel auf:
  
  in welcher A
  
  ist und B dasselbe wie A ist, oder B H ist oder ein verzweigtes oder unverzweigtes C₁-C₁₆-Alkyl ist, wobei das Alkyl Hydroxy-, Ether- oder Estergruppen enthalten kann, und R2, R3, R4, R5 und R6 H, OH, NH₂, COOH, SO₃H, verzweigtes oder unverzweigtes C₁-C₁₂-Alkyl, Acyl, NO₂, CN, Cl, CF₃, NOH-CO-Phenyl, C₁-C₆-Co-NOH-A, CO-NOH-A, COR₁₂, Phenyl-CO-NOH-A, OR₇, NR₈R₉, COOR₁₀ oder NOH-CO-R₁₁ sind, wobei R7, R8, R9, R10 und R11 verzweigtes oder unverzweigtes C₁-C₁₂-Alkyl oder Acyl sind. Innerhalb dieser Gruppe von Verstärkern sind besonders bevorzugte Verstärker ausgewählt aus der Gruppe, bestehend aus 4-Nitrobenzoesäure-N-Hydroxyanilid; 4-Methoxybenzoesäure-N-Hydroxyanilid; N,N'-Dihydroxy-N,N'-diphenylterephthalamid; Decansäure-N-hydroxyanilid; N-Hydroxy-4-cyanoacetanilid; N-Hydroxy-4-acetylacetanilid; N-Hydroxy-4-hydroxyacetanilid; N-Hydroxy-3-(N'-hydroxyacetamid)acetanilid; 4-Cyanobenzoesäure-N-hydroxyanilid; N-Hydroxy-4-nitroacetanilid; und N-Hydroxyacetanilid.
• – Anorganische Enzymaktivatoren oder -verstärker können ebenfalls relevant sein. Insbesondere kann die Gegenwart von anorganischen Halogenidionen, wie Chlorid, Bromid und/oder Iodid, die antimikrobielle Wirkung einer Halogenperoxidase verstärken.
• – Dispersionsmittel, um einer wirksamen Suspension in einem geschmolzenen Wachs Stabilität zu verleihen.
• – Viskositätsmodifikationsmittel zum Bereitstellen einer geeigneten Viskosität, wodurch optimale Pump- und/oder Zerstäubungseigenschaften ermöglicht werden.
• – Inerte Füllstoffe.
• – Fasermaterialien.
• – Pigmente, wie organische Pigmente oder anorganische Pigmente, z.B. TiO₂.

Other optional ingredients that may be suitably incorporated into the particle may be selected from the following non-limiting list:

• - Stabilizing and / or protective agents. Stabilizing or protecting agents may fall into several categories: alkaline or neutral materials, reducing agents, antioxidants and / or salts of first transition metal series ions. Each of them can be used in conjunction with other protection means of the same or different categories. Examples of alkaline preservatives are alkali metal silicates, carbonates or bicarbonates which provide a chemical scavenging effect by active neutralization, eg oxidants. Examples of reduction inhibitors are salts of sulfite, thiosulfite or thiosulfate, while examples of antioxidants are ascorbic acid, methionine, butylated hydroxytoluene (BHT) or butylated hydroxyanisole (BHA). Particularly preferred agents are salts of thiosulfates, for example sodium thiosulfate. Useful enzyme stabilizers, particularly for protease enzymes, may be borates, borax, formates, di- and tricarboxylic acids, and reversible enzyme inhibitors, such as organic compounds having sulfhydryl groups, or alkylated or arylated boric acids. Examples of boron-based stabilizers are found in WO 96/21716, whereas a preferred boron-based stabilizer is 4-formylphenylboronic acid or derivatives thereof described in WO 96/41859, both disclosures of which are incorporated herein by reference. Still other examples of useful enzyme stabilizers are gelatin, casein, polyvinylpyrrolidone (PVP) and skimmed milk powder.
• Enzyme activators and cofactors that can be used in the washing process to activate or enhance the action of the enzyme. Various organic enhancers or activators that act as electron donors for oxidoreductase enzymes for various purposes, such as bleaching or antimicrobial activity, are known in the art (eg, WO 94/12620, WO 94/12621, WO 95/01626 and WO 96/00179 ) and can be suitably incorporated into the enzyme particle. A group of preferred organic enhancers are phenolic compounds (alkylsyringates) of the formula:
  
  wherein the letter A in the formula denotes a group such as -D, -CH = CH-D, -CH = CH-CH = CH-D, -CH = ND, -N = ND or -N = CH-D, wherein D is selected from the group consisting of -CO-E, -SO ₂ -E, -N-XY and -N ⁺ -XYZ, where E can be -H, -OH, -R or -OR and X and Y. and Z may be identical or different and selected from -H and -R; wherein R is a C ₁ -C ₁₆ alkyl, preferably a C ₁ -C ₈ alkyl, which alkyl may be saturated or unsaturated, branched or unbranched and optionally substituted with a carboxy, sulfo or amino group; and B and C may be the same or different and selected from C _m H _{2m + 1} , where m = 1, 2, 3, 4 or 5. In the above-mentioned formula, A may be located in metast position to the hydroxy group rather than in the parent position as shown. In particular embodiments of the invention, the enzyme activator or enhancer is selected from the group having the formula:
  
  in which A is a group such as -H, -OH, -CH ₃ , -OCH ₃ , -O (CH ₂ ) _n CH ₃ , where n = 1, 2, 3, 4, 5, 6, 7 or 8 , Another preferred group of well-functioning organic enzyme activators or enhancers comprises a -CO-NOH group and has the following formula:
  
  in which A
  
  and B is the same as A, or is BH or a branched or unbranched C ₁ -C ₁₆ -alkyl, wherein the alkyl may contain hydroxy, ether or ester groups, and R 2, R 3, R _4, R 5 and R 6 are H, OH, NH ₂ , COOH, SO ₃ H, branched or unbranched C ₁ -C ₁₂ -alkyl, acyl, NO ₂ , CN, Cl, CF ₃ , NOH-CO-phenyl, C ₁ -C ₆ -CO-NOH- A, CO-NOH-A, COR ₁₂ , phenyl-CO-NOH-A, OR ₇ , NR ₈ R ₉ , COOR ₁₀ or NOH-CO-R ₁₁ , wherein R ₇ , R _8, R ₉ , R ₁₀ and R ₁₁ are branched or unbranched C ₁ -C ₁₂ alkyl or acyl. Within this group of enhancers, particularly preferred enhancers are selected from the group consisting of 4-nitrobenzoic acid N-hydroxyanilide; 4-methoxybenzoic acid-N-hydroxyanilide; N, N'-dihydroxy-N, N'-diphenylterephthalamide; Decanoic acid-N-hydroxyanilide; N-hydroxy-4-cyanoacetanilide; N-hydroxy-4-acetylacetanilid; N-hydroxy-4-hydroxyacetanilide; N-hydroxy-3- (N'-hydroxyacetamide) acetanilide; 4-cyanobenzoic acid-N-hydroxyanilide; N-hydroxy-4-nitroacetanilide; and N-hydroxyacetanilide.
• Inorganic enzyme activators or enhancers may also be relevant. In particular, the presence of inorganic halide ions such as chloride, bromide and / or iodide can enhance the antimicrobial effect of a haloperoxidase.
• Dispersing agent to impart stability to an effective suspension in a molten wax.
• Viscosity modifier to provide a suitable viscosity, thereby enabling optimum pumping and / or atomizing properties.
• - Inert fillers.
• - Fiber materials.
• Pigments, such as organic pigments or inorganic pigments, eg TiO ₂ .

coatings

Around the formation of active dust from the particles of the invention Hand to diminish the particles in a dry solid form can the particles suitably with one or more coating layers, which surrounds the solid wax matrix comprising the active ingredient which is also an additional one Protection of the active ingredient from components in the environment, e.g. in the liquid phase can provide. As a result, the invention also provides particles invention provided with one or more coating layers, which surround the solid wax matrix are coated. To reduce dusting is the coating preferably substantially free of active agent, e.g. the coating contains less as 6 milligrams of active ingredient, such as enzyme per gram of coating. However, one can or several coating layers, the extra May comprise active substances, is applied between the wax matrix particle and the outer coating layer become. Useful coatings for particles of the invention are in the art, as in the international Patent Application DK99 / 00364 (unpublished). In a preferred embodiment includes the coating also a wax as described above.

It it is only necessary that the coating is intact when handling the enzyme particles in dry form, since upon addition of the particles to a liquid phase, an effective Dust formation is eliminated from the particles. As a result, coating materials can be used selected be in the liquid Phase of the liquid Composition soluble or dispersible. In a preferred embodiment is the coating material in the liquid Phase of the liquid Composition insoluble or undispersible, and in a second embodiment, the coating material in the liquid Phase of the liquid Composition soluble or dispersible. The coating can by conventional Coating method, e.g. in a blender granulator or a Fluidized bed, e.g. by spraying of the coating material or a solution or dispersion thereof on the particles of the invention become.

method for the production of enzyme particles

The The invention also relates to processes for the production of particles of Invention.

• (a) Herstellen eines Gemischs I, umfassend ein erstes Wachs, vorzugsweise in geschmolzener Form, und ein oder mehrere zusätzliche Wachse, vorzugsweise in geschmolzener Form, mit einer niedrigeren oder höheren tatsächlichen Dichte als das erste Wachs, oder
• (b) Herstellen eines Gemischs II, umfassend ein erstes Wachs, vorzugsweise in geschmolzener Form und ein Dichtemodifikationsmittel, oder
• (c) Herstellen eines Gemischs III, umfassend ein erstes Wachs, vorzugsweise in geschmolzener Form und ein oder mehrere zusätzliche Wachse vorzugsweise in geschmolzener Form mit einer niedrigeren oder höheren tatsächlichen Dichte als das erste Wachs und ein Dichtemodifikationsmittel,
• (d) Dispergieren oder Lösen eines Wirkstoffs in den Gemischen I oder II oder III,
• (e) Herstellen von wirkstoffhaltigen Teilchen durch Verfestigen der in Schritt (d) erhaltenen Dispersion oder Lösung.

We have discovered a method of making particles of the invention wherein the actual density of the finished particles can be adjusted to a desired value. The method comprises the following steps:

• (a) preparing a mixture I comprising a first wax, preferably in molten form, and one or more additional waxes, preferably in molten form, having a lower or higher actual density than the first wax, or
• (b) preparing a mixture II comprising a first wax, preferably in molten form, and a density modifier, or
• (c) preparing a mixture III comprising a first wax, preferably in molten form and one or more additional waxes preferably in molten form having a lower or higher actual density than the first wax and a density modifier,
• (d) dispersing or dissolving an active substance in the mixtures I or II or III,
• (e) preparing active substance-containing particles by solidifying the dispersion or solution obtained in step (d).

In an embodiment For example, a step (a) method is preferred while in a further embodiment a step (b) comprehensive method is preferred while in a still other embodiment a step (c) comprehensive method is preferred. The invention Also includes products through a process involving step (a), (d) and (e) or (b), (d) and (e) or (c), (d) and (e).

drugs Waxes and density modifiers are described above.

• (f) Zerstäuben der Dispersion oder Lösung in Tröpfchen und
• (g) Verfestigen der Tröpfchen zu festen Teilchen durch Abkühlen der Tröpfchen,

und diesem Verfahren können vorzugsweise auch ein oder mehrere Kühlschritte (1F) und wahlweise Fraktionierungs- und Rückführschritte (1H und I) folgen.Process (e) is preferably carried out in a so-called spray-cooling or spray-quenching process as known in the art, comprising the steps of:

• (f) atomizing the dispersion or solution into droplets and
• (g) solidifying the droplets to solid particles by cooling the droplets,

and this process may preferably also include one or more cooling steps ( 1F ) and optionally fractionation and recycling steps ( 1H and I) follow.

The active ingredient may be applied to the molten wax by mixing a preferably purified solid active in the molten wax. In the preferred embodiment, in which the active ingredient is an enzyme, the enzyme is preferably a crystalline or amorphous enzyme preparation (as described in WO 91/09943). In a more preferred embodiment, the active ingredient and optionally other ingredients are in a dry powder form, such as spray-dried products, which are dispersed or suspended in the molten wax. Atomization of the molten wax may be achieved in a variety of ways, including atomization using either a high speed rotary atomizer, a pressure nozzle, a pneumatic nozzle, or an ultrasonic nozzle such as course material from the microencapsulation seminar held by the Center for Professional Advancement from 9 to 11 May 1990 in Amsterdam. The solidification of the droplets by cooling may advantageously be carried out in a cooling vessel, such as a tower, wherein the atomized dispersion or solution of the enzyme in molten wax is introduced into a cold air stream at the top of the tower and the solidification of the droplets takes place, while the droplets move through the cold airstream to the bottom of the tower. The mixture of molten wax, enzyme, and optionally other ingredients is preferably added to the nebulizer at a temperature of at least 30 ° C above the solidification initiation temperature to prevent inadvertent solidification and clogging in the feed tubes and in the nebulizer. The amount and temperature of the air used to cool the molten wax mixture should be adjusted so that they can remove sufficient heat from the molten wax mixture to facilitate solidification (sensitive heat of the liquid, latent heat of melting the solid, and sensitive heat of the solid) , In a preferred embodiment, the temperature of the air leaving the cooling tower ( 1D ) about 5 ° C below the temperature of the solid particles leaving the cooling tower.

The general technique of spray cooling or spray quenching is known in the art and may be carried out using known apparatuses as described in K. Masters, Applications in the chemical industry, Section 14.10.1, pp. 565-566, Spray Drying Handbook, 3. Edition 1979, George Goodwin Ltd. London ISBN 0-7114-4924-4 / John Wiley & Sons, New York. A schematic overview of a spray cooling process is in 1 shown.

By Apply spray cooling The preparation of the particle of the invention can be very spherical particles achieved with one size by adjusting the atomization and cooling conditions can be adjusted. helpful Particle sizes are in the range of about 20 to about 2000 microns, preferably between about 100 to about 1000 μm, e.g. between about 200 to about 600 microns. After determining the sputtering and cooling conditions can Particles with a narrow size distribution which eliminates the need for separation, e.g. by Seven, and returning over and with great Minimizes particles. In a preferred embodiment, the particles before a sieving and / or return step a SPAN value below about 2.0, preferably below about 1.2, more preferably below about 1.0, stronger preferably below about 0.8 and more preferably below about 0.6 on.

The SPAN value is a measure of the width of the particle size distribution (PSD) and defined as: (D90 - D10) / D50 wherein the D values express the mean mass diameter of the individual particles. The mean mass diameter, D50, is the diameter at which 50% by mass of the enzyme particles have a smaller diameter, while 50% by mass has a larger diameter. The values D10 and D90 are the diameters at which 10 and 90 mass% of the particles have a smaller diameter than the value in question. The smaller the SPAN value, the narrower the particle size distribution.

For purposes In the present invention, the particle size distribution is normal as close as possible. The SPAN of a granule product according to the invention is therefore typically not more than 2.6, preferably not more than about 2.0, stronger preferably not more than about 1.5, and most preferably not more than about 1.0.

When Alternatively, the invention also includes the preferred method for producing particles by preparing a dispersion Active ingredient and optionally other ingredients in one or more molten Growing, solidifying the wax (s) and grinding / breaking the solid wax matrix into particles and optionally rounds of the particles, e.g. in a Marumerizer, before the optional coating of the particles.

coating process

• (a) Aufwirbeln der Teilchen der Erfindung in einer Wirbelbettapparatur,
• (b) Einbringen eines flüssigen Mediums, umfassend ein Überzugsmaterial, auf die Teilchen der Erfindung durch Zerstäuben des flüssigen Mediums in das Wirbelbett derart, dass sich das Überzugsmaterial als feste Überzugsschicht auf den Teilchen der Erfindung abscheidet, und
• (c) Entfernen von flüchtigen Bestandteilen des flüssigen Mediums von den beschichteten Teilchen.

The coating of the prepared enzyme-containing particles can be achieved by any conventional coating method, such as in a fluid bed coater, the method comprising:

• (a) fluidizing the particles of the invention in a fluidized bed apparatus,
• (b) introducing a liquid medium comprising a coating material onto the particles of the invention by sputtering the liquid medium into the fluidized bed such that the coating material deposits as a solid coating layer on the particles of the invention, and
• (c) removing volatiles of the liquid medium from the coated particles.

Liquid compositions

The The invention also relates to a liquid A composition comprising solid particles dispersed therein Invention as described above. Also included in the Invention is a process for producing a liquid composition, comprising the step of dispersing solid particles of Invention in a liquid Phase.

The liquid Phase of the composition is at 20 ° C in liquid form. Preferably the particles of the invention are in the liquid phase of the composition essentially stable dispersed.

For purposes the invention is the term "im Substantially stable dispersion "of Particles in a liquid Composition defined as a dispersion in which visual no separation of the particles from the liquid phase, through which the particles concentrate in one part of the composition at one at 20 ° C held sample of the dispersion, for a period of at least 48 hours can be observed. In a more restricted and preferred definition of the separation is visual no separation of the Enzyme particles from the liquid Phase at one at 20 ° C held sample of the dispersion for a period of at least one, preferably two weeks to observe.

In a preferred embodiment of the invention, the active ingredient in the particle is an enzyme and the liquid composition is a liquid detergent composition. In order for an enzyme particle to remain dispersed in a liquid detergent phase, an important property of the particle is its true density. If the enzyme particle has an actual density well in excess of the actual density of the liquid detergent phase, the enzyme particle will not remain dispersed in the liquid detergent phase over time, but will move to the bottom of the liquid phase and form an enzyme particle sediment, influenced by gravitational forces , However, if the actual density of the enzyme particles is significantly lower than the actual density of the liquid detergent phase, the enzyme particles concentrate on the surface. It is considered that these motions are of course dependent on the viscosity of the liquid phase in which the particles are dispersed and the size of the particles, ie the higher the viscosity of the liquid phase and the smaller the size, the greater the difference in the actual density between the liquid phase and the enzyme particles may be allowed to keep the enzyme particles dispersed. In a preferred embodiment of the invention thus includes the liquid detergent composition of the invention, the enzyme particles, which amount to a true density between about plus 0.5 g / cm ³ to about minus 0.5 g / cm ³ of the actual sealing of the liquid detergent phase. This means that, if the detergent has a true density of for example 2 g / cm ^3, should the actual density of the enzyme particles is between about 1.5 g / cm ³ to about 2.5 g / cm ^3. Of course, preferably, a smaller difference between the true densities of the enzyme particles and the liquid phase is better, there is the true density of the enzyme particles is between about plus 0.3 g / cm ³ to about minus 0.3 g / cm ^3, for example between about 0 , 1 g / cm ³ to about minus 0.1 g / cm ^{3 of} the actual density of the liquid detergent phase. For small enzyme-containing particles, eg for sizes between 50 to 200 microns, the difference in actual density between the enzyme particles and the liquid phase may be greater depending on the viscosity of the liquid phase. For such small particles, the actual density of the particles may be outside the range of the actual density of the liquid phase plus or minus 0.5 g / cm ³ . In this embodiment of the invention, particles having a size such as between 50 to 200 microns may have an actual density, for example in the ranges plus or minus 0.5-1.5 g / cm ^{3 of} the actual density of the liquid phase.

Of the Desire and the need for enzyme particles with a strongly controlled actual Density, which is the formation of essentially stable dispersions of enzyme particles in a liquid Enable detergent phase, encouraged us, the liquid Detergent composition of the invention to develop.

Liquid detergents

The liquid Detergent composition of the invention is preferably substantially from non-aqueous (or anhydrous) texture. The term "substantially non-aqueous" means as in This context uses that, while very small amounts of water in such preferred compositions as an impurity in be introduced the essential or optional components can, the amount of water in non-aqueous liquid Detergent compositions of the invention by no means about 5% by weight exceed the composition should. Stronger Preferably, the water content of the non-aqueous detergent composition comprises less than about 1% by weight.

surfactant medium

The Detergent composition of the invention comprises one or more surfactants Agents that are non-ionic, including semi-polar and / or anionic and / or cationic and / or zwitterionic. The Amount of surface active Blend component of the detergent compositions here can ever by nature and amount of other compositional components and depending on the desired rheological properties of the final formed composition vary. In general, this surface-active mixture in a Amount comprising about 0.1 to 90% by weight of the composition used. Stronger Preferably, the surfactant comprises Mixture about 10 to 60 wt .-% of the composition.

When included herein, the detergent typically contains from about 1 to about 40% of an anionic surfactant such as linear alkyl benzene sulfonate, alpha olefin sulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfofatty acid methyl ester, alkyl or alkenyl succinic acid or soap. Highly preferred 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. Especially preferred are the linear straight-chain sodium and potassium alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is about 11-14. Sodium C ₁₁ -C ₁₄ , for example C ₁₂ -LAS is particularly preferred. Other useful anionic surfactants are described in WO 99/0478, pages 11 to 13, incorporated herein by reference.

If included here contains the detergent usually from about 0.2 to about 40% of a nonionic surfactant Such as alcohol ethoxylate, nonyl phenol ethoxylate, alkyl polyglycoside, Alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy or N-acyl-N-alkyl derivatives of glucosamine ("glucosamides"). Such useful nonionic surfactant Means are further described in WO 99/0478, pages 13 to 14, here below Reference incorporated.

The Detergent may also be ampholytic and / or zwitterionic surfactant Contain funds.

A typical listing of anionic, nonionic, ampholytic and zwitterionic surfactants is in US 3,664,961 , issued to Noris on May 23, 1972.

Non-aqueous liquid thinner

To the Forming the liquid Phase of the detergent compositions may be as described hereinbefore surfactants Means (mixture) with a non-aqueous liquid Diluents, like a liquid Alcohol alkoxylate material or a non-aqueous organic solvents with low polarity, as described in WO 99/0478, pages 14 to 17, herein incorporated by reference introduced, combined. (One) used non-aqueous (s), organic solvent (s) with low polarity should (of course) with other composition components, e.g. Enzymes and / or Bleaches and / or activators used in the liquid detergent compositions used here, compatible and be non-reactive. Such a solvent component becomes generally in an amount of about 1 to 60% by weight of the composition used. Stronger Preferably, the non-aqueous organic solvents with low polarity about 5 to 40% by weight of the composition, more preferably about 10 to 25% by weight of the composition.

EDDS

The Compositions of the invention may be about 0.01 to about 10%, preferably about 0.05 to about 2% ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted Ammonium salts thereof or mixtures thereof. Preferred EDDS compounds for liquid detergent compositions are the free acid form and the sodium or potassium salts thereof. EDDS are in the US patent 4,704,233.

EDDS improves the efficacy of enzymes, especially amylases, in liquid non-aqueous Detergent compositions by dilution of the wash liquor. Without to be bound by theory, it is believed that ethylenediamine-N, N'-disuccinic acid or their salts act to bind heavy metal ions, thereby preventing is that heavy metal ions bind to the site of action of the enzyme. The binding of heavy metal ions to the site of action of the enzyme leads to Formation of free OH radicals in the enzyme, which leads to the destruction of the Enzyme leads.

chelating agent

The Liquid detergent compositions according to the invention can also 0-65 Wt .-% of other chelating agents included. Such chelating agents can selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, diphosphate, Triphosphate, carbonate, citrate, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl or alkenyl succinic 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.

enzyme stabilizers

The The enzyme (s) in the particles of the invention may also be conventional using stabilizing agents in the liquid phase, e.g. a polyol such as propylene glycol or glycerine, a sugar or sugar alcohol, of lactic acid, boric acid or a boric acid derivative, e.g. an aromatic borate ester, or a phenylboronic acid derivative, such as 4-formylphenylboronic acid, be stabilized, and the composition may be such. in WO 92/19709 and WO 92/19708.

It becomes current considered that in the detergent compositions any Enzyme, in particular the enzyme of the invention, in an amount corresponding to 0.01-100 mg enzyme protein per liter of wash liquor, preferably 0.05-5 mg enzyme protein per liter of wash liquor, in particular 0.1-1 mg of enzyme protein per liter Washing liquor, can be added.

The Enzyme of the invention may additionally in the detergent formulations disclosed in WO 97/07202, here incorporated by reference.

Other particulate material as enzyme particles

The liquid detergent compositions of the invention may further comprise, in addition to the enzyme particles of the invention, a solid phase of particulate material which is dispersed or suspended in the liquid phase. In general, such a particulate material is in size rich from about 0.1 to 1500 microns. More preferably, such a material is in the size range of about 5 to 500 microns.

• – Bleichmittel, einschließlich festes Peroxidbleichmittel. Der besonders bevorzugte Typ an teilchenförmigem Material, der zum Bilden der festen Phase der Detergenszusammensetzungen hier nützlich ist, umfasst Teilchen aus einem Peroxidbleichmittel. Derartige Peroxidbleichmittel können organischer oder anorganischer Natur sein. Anorganische Peroxidbleichmittel werden häufig in Kombination mit einem Bleichaktivator verwendet. Nützliche anorganische Peroxidbleichmittel schließen Perborat- oder Percarbonatverbindungen ein. Nützliche organische Peroxidbleichmittel schließen Percarbonsäurebleichmittel und/oder Peroxysäuren z.B. von Amid-, Imid- oder Sulfontyp ein. Geeignete Beispiele für Peroxidbleichmittel sind des Weiteren in WO 99/00478, Seite 18–19, hier unter Bezugnahme eingebracht, beschrieben. Werden Peroxidbleichmittel als gesamtes oder Teil des im Wesentlichen vorliegenden teilchenförmigen Materials verwendet, umfassen sie im Allgemeinen etwa 1 bis 30 Gew.-% der Zusammensetzung. Stärker bevorzugt umfassen Peroxidbleichmittel etwa 1 bis 20 Gew.-% der Zusammensetzung. Besonders bevorzugt liegen Peroxidbleichmittel bis zu einem Gehalt von etwa 3 bis 15 Gew.-% der Zusammensetzung vor.
• – Feste Bleichaktivatoren, wie ein Persäure-bildender Bleichaktivator, z.B. Tetraacetylethylendiamin oder Nonanoyloxybenzolsulfonat. Geeignete Beispiele für Bleichaktivatoren sind des Weiteren in WO 99/00478, Seite 19–20, hier unter Bezugnahme eingebracht, beschrieben. Falls verwendet, können Bleichaktivatoren etwa 0,5 bis 20 Gew.-%, stärker bevorzugt etwa 1 bis 10 Gew.-% der Zusammensetzung umfassen. Häufig werden Aktivatoren derart eingesetzt, dass das Molverhältnis von Bleichmittel zu Aktivator im Bereich von etwa 1:1 bis 10:1, stärker bevorzugt von etwa 1,5:1 bis 5:1 liegt. Zudem wurde gefunden, dass Bleichaktivatoren, falls sie mit bestimmten Säuren, wie Zitronensäure, agglomeriert sind, chemisch stabiler sind.
• – Teilchenförmige oberflächenaktive Mittel, die z.B. in den nicht-wässrigen flüssigen Detergenszusammensetzungen hier suspendiert werden können, schließen zusätzliche anionische oberflächenaktive Mittel ein, die in der nicht-wässrigen flüssigen Phase vollständig oder teilweise unlöslich sind. Der üblichste Typ an anionischem oberflächenaktivem Mittel mit derartigen Löslichkeitseigenschaften umfasst primäre oder sekundäre anionische oberflächenaktive Alkylsulfate. Derartige oberflächenaktive Mittel sind diejenigen, die durch die Sulfatierung von höheren C₈-C₂₀-Fettalkoholen hergestellt werden. Weitere Beispiele für derartige nützliche oberflächenaktive Mittel sind in WO 99/00478, Seite 21–22, hier unter Bezugnahme eingebracht, beschrieben. Falls als gesamtes oder als Teil des erforderlichen teilchenförmigen Materials verwendet, umfassen zusätzliche anionische oberflächen aktive Mittel, wie Alkylsulfate, im Allgemeinen etwa 1 bis 10 Gew.-% der Zusammensetzung, stärker bevorzugt etwa 1 bis 5 Gew.-% der Zusammensetzung. Alkylsulfat, das als gesamtes oder als Teil des teilchenförmigen Materials verwendet wird, wird hergestellt und den Zusammensetzungen hier getrennt von dem unalkoxylierten Alkylsulfatmaterial, das einen Teil des oberflächenaktiven Alkylethersulfatbestandteils bilden kann, der im Wesentlichen als Teil der flüssigen Phase hier verwendet wird, zugesetzt.
• – Festes organisches Gerüststoffmaterial. Derartige Verbindungen dienen dazu, den Wirkungen von Calcium oder eines anderen Ions, der Wasserhärte, die während der Wasch- und/oder Bleichverwendung der Zusammensetzungen hier anzutreffen ist, entgegenzuwirken. Beispiele für derartige Materialien schließen Alkalimetallcitrate, -succinate, -malonate, Fettsäuren, Carboxymethylsuccinate, Carboxylate, Polycarboxylate und Polyacetylcarboxylate ein. Spezifische Beispiele schließen Natrium-, Kalium- und Lithiumsalze von Oxydibernsteinsäure, Mellitsäure, Benzolpolycarbonsäuren und Zitronensäure ein. Andere Beispiele für organische Maskierungsmittel vom Phosphonattyp sind diejenigen, die von Monsanto unter der Dequest-Marke vertrieben wurden, und Alkanhydroxyphosphonate. Citratsalze sind stark bevorzugt. Andere geeignete organische Gerüststoffe schließen die Polymer und Copolymere mit höherem Molekulargewicht, von welchen es bekannt ist, dass sie Gerüststoffeigenschaften aufweisen, ein. Zum Beispiel schließen derartige Materialien die entsprechende Polyacrylsäure-, Polymaleinsäure- und Polyacryl/Polymaleinsäure-Copolymere und deren Salze, wie diejenigen, die unter der Sokalan-Marke von BASF vertrieben werden, ein. Ein anderer geeigneter Typ an organischem Gerüststoff umfasst die wasserlöslichen Salze von höheren Fettsäuren, d.h., „Seifen". Diese schließen Alkalimetallseifen, wie die Natrium-, Kalium-, Ammonium- und Alkylammoniumsalze von höheren Fettsäuren, enthaltend etwa 8 bis etwa 24 Kohlenstoffatome, und vorzugsweise etwa 12 bis etwa 18 Kohlenstoffatome, ein. Seifen können durch direktes Verseifen von Fetten und Ölen oder durch die Neutralisation von freien Fett säuren hergestellt werden. Besonders nützlich sind die Natrium- und Kaliumsalze oder Gemische von Fettsäuren, die von Kokosöl und Talg abgeleitet sind, d.h. Natrium- und Kaliumtalg und Kokosnussseife. Werden sie als das gesamte oder ein Teil des erforderlichen teilchenförmigen Materials verwendet, können unlösliche organische Detergensgerüststoffe im Allgemeinen etwa 1 bis 20 Gew.-% der Zusammensetzungen hier umfassen. Stärker bevorzugt kann ein derartiges Gerüststoffmaterial etwa 4 bis 10 Gew.-% der Zusammensetzung umfassen.
• – Feste anorganische Alkalinitätsquellenverbindungen können ebenfalls in die Detergenszusammensetzung der Erfindung eingebracht werden. Derartige Verbindungen können ein Material umfassen, das dazu dient, wässrige Waschlösungen, die aus Zusammensetzungen der Erfindung gebildet werden, im Allgemeinen eine alkalischere Natur zu verleihen. Derartige Materialien können ebenfalls als Detergensgerüststoffe, d.h. Materialien, die der negativen Wirkung von Wasserhärte auf die Waschleistung entgegenwirken, wirken oder auch nicht. Beispiele für geeignete Alkalinitätsquellen schließen wasserlösliche Alkalimetallcarbonate, -bicarbonate, -borate, -silicate und -metasilicate ein. Obwohl aus ökologischen Gründen nicht bevorzugt, können auch wasserlösliche Phosphatsalze als Alkalinitätsquellen verwendet werden. Diese schließen Alkalimetallpyrophosphate, -orthophosphate, -polyphosphate und -phosphonate ein. Unter allen diesen Alkalinitätsquellen sind Alkalimetallcarbonate, wie Natriumcarbonat, besonders bevorzugt. Die Alkalinitätsquelle, falls sie in Form eines hydratisierbaren Salzes vorliegt, kann auch als Trockenmittel in einer nicht-wässrigen flüssigen Detergenszusammensetzung dienen. Die Gegenwart einer Alkalinitätsquelle, die auch ein Trockenmittel ist, kann in Bezug auf die chemische Stabilisierung derjenigen Zusammensetzungsbestandteile, wie das Peroxidbleichmittel, das für eine Deaktivierung durch Wasser empfänglich sein kann, Nutzen bereitstellen. Falls als gesamtes oder als Teil des teilchenförmigen Materialbestandteils verwendet, umfassen die Alkalinitätsquellenverbindungen im Allgemeinen etwa 1 bis 15 Gew.-% der Zusammensetzungen hier. Stärker bevorzugt kann die Alkalinitätsquelle etwa 2 bis 10 Gew.-% der Zusammensetzung umfassen. Derartige Materialien sind, obwohl wasserlöslich, im Allgemeinen in einer nicht-wässrigen Detergenszusammensetzung unlöslich, und derartige Materialien werden im Allgemeinen in einer nicht-wässrigen flüssigen Phase in Form von gesonderten Teilchen dispergiert.

The particulate material used herein may include one or more types of detergent composition ingredients that are substantially insoluble in particulate form in the liquid phase of the composition. The types of particulate materials which may be used may be selected from the following non-limiting list of useful ingredients.

• Bleach, including solid peroxide bleach. The most preferred type of particulate material useful herein for forming the solid phase of the detergent compositions herein comprises particles of a peroxygen bleach. Such peroxide bleaching agents may be organic or inorganic in nature. Inorganic peroxide bleaching agents are often used in combination with a bleach activator. Useful inorganic peroxygen bleaches include perborate or percarbonate compounds. Useful organic peroxygen bleaches include percarboxylic acid bleaches and / or peroxyacids, eg of amide, imide or sulfone type. Suitable examples of peroxygen bleaches are further described in WO 99/00478, pages 18-19, incorporated herein by reference. When peroxygen bleaches are used as all or part of the substantially particulate material present, they generally comprise from about 1 to 30% by weight of the composition. More preferably, peroxygen bleaches comprise about 1 to 20 percent by weight of the composition. More preferably, peroxygen bleaches are present at a level of from about 3 to 15 percent by weight of the composition.
• Solid bleach activators, such as a peracid-forming bleach activator, eg tetraacetylethylenediamine or nonanoyloxybenzenesulfonate. Suitable examples of bleach activators are further described in WO 99/00478, pages 19-20, incorporated herein by reference. If used, bleach activators may comprise about 0.5 to 20 wt%, more preferably about 1 to 10 wt% of the composition. Frequently, activators are employed such that the molar ratio of bleach to activator ranges from about 1: 1 to 10: 1, more preferably from about 1.5: 1 to 5: 1. In addition, it has been found that bleach activators, if agglomerated with certain acids, such as citric acid, are more chemically stable.
• Particulate surfactants which may be suspended in, for example, the non-aqueous liquid detergent compositions herein include additional anionic surfactants which are wholly or partially insoluble in the non-aqueous liquid phase. The most common type of anionic surfactant having such solubility properties comprises primary or secondary anionic alkyl surface-active sulfates. Such surfactants are those made by the sulfation of higher C ₈ -C ₂₀ fatty alcohols. Further examples of such useful surfactants are described in WO 99/00478, pages 21-22, incorporated herein by reference. If used as all or as part of the required particulate material, additional anionic surfactants include active agents, such as alkyl sulfates, generally from about 1 to 10 weight percent of the composition, more preferably from about 1 to 5 weight percent of the composition. Alkyl sulfate, used as all or as part of the particulate material, is prepared and added to the compositions herein separately from the unalkoxylated alkyl sulfate material, which may form part of the alkyl ether sulfate surfactant component used herein as part of the liquid phase.
• - Solid organic builder material. Such compounds serve to counteract the effects of calcium or other ion, the water hardness, encountered during the washing and / or bleaching use of the compositions herein. Examples of such materials include alkali metal citrates, succinates, malonates, fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid. Other examples of phosphonate-type organic sequestrants are those sold by Monsanto under the Dequest trademark and alkane hydroxy phosphonates. Citrate salts are highly preferred. Other suitable organic builders include the higher molecular weight polymers and copolymers that are known to have builder properties. For example, such materials include the corresponding polyacrylic, polymaleic and polyacrylic / polymaleic acid copolymers and their salts, such as those sold under the Sokalan trademark of BASF. Another suitable type of organic builder comprises the water-soluble salts of higher fatty acids, ie, "soaps." These include alkali metal soaps, such as the sodium, potassium, ammonium and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and Preferably, from about 12 to about 18 carbon atoms, soaps can be made by directly saponifying fats and oils, or by neutralizing free fatty acids Particularly useful are the sodium and potassium salts or mixtures of fatty acids derived from coconut oil and tallow ie, sodium and potassium tallow and coconut soap.When they are required as the whole or part of In general, insoluble organic detergent builders generally comprise about 1 to 20% by weight of the compositions herein. More preferably, such builder material may comprise about 4 to 10% by weight of the composition.
• Solid inorganic alkalinity source compounds can also be incorporated into the detergent composition of the invention. Such compounds may comprise a material which serves to render aqueous wash solutions formed from compositions of the invention generally more alkaline in nature. Such materials may or may not act as detergent builders, ie, materials that counteract the adverse effect of water hardness on detergency. Examples of suitable alkalinity sources include water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates. Although not preferred for environmental reasons, water-soluble phosphate salts can also be used as alkalinity sources. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Among all of these alkalinity sources, alkali metal carbonates such as sodium carbonate are particularly preferred. The alkalinity source, if in the form of a hydratable salt, may also serve as a desiccant in a non-aqueous liquid detergent composition. The presence of a source of alkalinity, which is also a desiccant, may provide benefits in terms of chemical stabilization of those compositional ingredients, such as the peroxygen bleach, which may be susceptible to deactivation by water. When used as a whole or as part of the particulate material component, the alkalinity source compounds generally comprise from about 1 to 15% by weight of the compositions herein. More preferably, the source of alkalinity may comprise about 2 to 10% by weight of the composition. Such materials, although water-soluble, are generally insoluble in a non-aqueous detergent composition, and such materials are generally dispersed in a non-aqueous liquid phase in the form of discrete particles.

optional Detergent ingredients

• – Anorganische Detergensgerüststoffe. Die Detergenszusammensetzung der Erfindung kann auch wahlweise einen oder mehrere Typen von anorganischen Detergensgerüststoffen abgesehen von denjenigen, die hier vorstehend aufgelistet sind, die auch als Alkalinitätsquellen oder Chelatbildner wirken, enthalten. Derartige optionale anorganische Gerüststoffe können zum Beispiel Aluminiumsilicate, wie Zeolithe, einschließen. Aluminiumsilcatzeolithe und deren Verwendung als Detergensgerüststoffe sind vollständiger in Corkill et al., US-Patent Nr. 4,605,509; erteilt am 12. August 1986, wobei die Offenbarung davon hier unter Bezugnahme eingebracht ist, erörtert. Auch sind kristalline geschichtete Silicate, wie diejenigen, die in diesem '509-US-Patent erörtert sind, zur Verwendung in den Detergenszusammensetzungen hier geeignet. Falls verwendet, können optionale anorganische Detergensgerüststoffe etwa 2 bis 15 Gew.-% der Zusammensetzungen hier umfassen.
• – Verdickungs-, Viskositätssteuerungs- und/oder Dispersionsmittel. Die Detergenszusammensetzung der Erfindung kann auch wahlweise ein polymeres Material enthalten, das zum Verbessern des Vermögens der Zusammensetzung zum Halten ihrer festen teilchenförmigen Bestandteile in Suspension dient. Derartige Materialien können demnach als Verdickungsmittel, Viskositätssteuerungsmittel und/oder Dispersionsmittel wirken. Derartige Materialien sind häufig polymere Polycarboxylate, können jedoch andere polymere Materialien, wie Polyvinylpyrrolidon (PVP), Carboxymethylcellulose, Poly(ethylenglycol), Poly(vinylalkohol), Poly(vinyl-pyridin-N-oxid), Poly(vinylimidazol) und polymere Aminderivate, wie quaternisierte, ethoxylierte Hexamethylendiamine, einschließen. Polymere Polycarboxylat-Materialien können durch Polymerisieren oder Copolymerisieren von geeigneten ungesättigten Monomeren, vorzugsweise in deren Säureform, hergestellt werden. Ungesättigte monomere Säuren, die zum Bilden von geeigneten polymeren Polycarboxylaten polymerisiert werden können, schließen Acrylsäure, Maleinsäure (oder Maleinsäureanhydrid), Fumarsäure, Itaconsäure, Aconitsäure, Mesaconsäure, Citraconsäure, Methylenmalonsäure und Laurylmethacrylsäure ein. Die Gegenwart in den polymeren Polycarboxylaten hier von monomeren Segmenten, enthaltend keine Carboxylatreste, wie Vinylmethylether, Styrol, Ethylen usw., ist geeignet, mit der Maßgabe, dass derartige Segmente nicht mehr als etwa 40 Gew.-% des Polymers bilden. Besonders geeignete polymere Polycarboxylate können von Acrylsäure abgeleitet sein. Derartige Polymere auf Acrylsäurebasis, die hier nützlich sind, sind die wasserlöslichen Salze von polymerisierter Acrylsäure. Das mittlere Molekulargewicht derartiger polymere in der Säureform liegt vorzugsweise im Bereich von etwa 2.000 bis 10.000, stärker bevorzugt von etwa 4.000 bis 7.000 und besonders bevorzugt von etwa 4.000 bis 5.000. Wasserlösliche Salze von derartigen Acrylsäurepolymeren können zum Beispiel die Alkalimetallsalze einschließen. Lösliche Polymere dieses Typs sind bekannte Materialien. Die Verwendung von Polyacrylaten dieses Typs in Detergenszusammensetzungen wurde zum Beispiel in Dieh-i, US-Patent 3,308,067, erteilt 7. März 1967, offenbart. Derartige Materialien können auch eine Gerüststofffunktion ausüben. Falls verwendet, sollten optionale Verdickungs-, Viskositätssteuerungs- und/oder Disper sionsmittel in den Zusammensetzungen hier bis zu einem Gehalt von etwa 0,1 bis 4 Gew.-% vorliegen. Stärker bevorzugt können derartige Materialien etwa 0,5 bis 2 Gew.-% der Detergenszusammensetzungen hier umfassen.
• – Optionale Aufheller, Schaumunterdrücker und/oder Parfüms. Die Detergenszusammensetzung der Erfindung hier kann wahlweise herkömmliche Aufheller, Schaumunterdrücker, Siliconöle, Bleichkatalysatoren und/oder Parfümmaterialien enthalten. Derartige Aufheller, Schaumunterdrücker, Siliconöle, Bleichkatalysatoren und Parfüms müssen natürlich mit den anderen Zusammensetzungsbestandteilen in der Umgebung der flüssigen Detergenszusammensetzung verträglich und nicht-reaktiv sein. Falls vorliegend, umfassen Aufheller, Schaumunterdrücker und/oder Parfüms typischerweise etwa 0,01 bis 5 Gew.-% der Zusammensetzungen hier. Geeignete Bleichkatalysatoren schließen die Komplexe auf Manganbasis, offenbart in US 5,246,621 , US 5,244,594 , US 5,114,606 und US 5,114,611 , ein.
• – Optionale organische Additive. Die Detergenszusammensetzung der Erfindung kann ein organisches Additiv enthalten. Ein bevorzugtes organisches Additiv ist hydriertes Rizinusöl und dessen Derivate. Hydriertes Rizinusöl ist ein im Handel erhältliches Erzeugnis, das zum Beispiel in verschiedenen Klassen unter der Marke CASTORWAX.RTM. von NL Industries, Inc., Highstown, New Jersey, vertrieben wird. Andere geeignete hydrierte Rizinusölderivate sind Thixcin R, Thixcin E, Thixatrol ST, Perchem R und Perchem ST. Ein besonders bevorzugtes hydriertes Rizinusöl ist Thixatrol ST. Das Rizinusöl kann als Gemisch zum Beispiel mit Stereamid zugesetzt werden. Das organische Additiv wird teilweise in einem nicht-wässrigen flüssigen Verdünnungsmittel gelöst. Zum Bilden der strukturierten flüssigen Phase, die für eine geeignete Phasenstabilität und akzeptable Rheologie erforderlich ist, liegt das organische Additiv im Allgemeinen mit einem Gehalt von etwa 0,05 bis 20 Gew.-% der flüssigen Phase vor. Stärker bevorzugt umfasst das organische Additiv etwa 0,1 bis 10 Gew.-% der flüssigen Phase der Detergenszusammensetzung der Erfindung.
• – Andere optionale Detergensinhaltsstoffe, wie Gewebeweichmacher, einschließlich Tone, Schaumverstärker, Antikorrosionsmittel, Schmutzsuspensionsmittel, Mittel gegen die Wiederablagerung von Schmutz, Farbstoffe, Bakterizide, Hydrotrope und Trübungshemmer.

The detergent may also contain other optional detergent ingredients. The optional ingredients can either dissolve in the liquid phase or be dispersed in the liquid phase in the form of fine particles or droplets. The types of materials that may be used may be selected from the following non-limiting list of useful ingredients:

• Inorganic detergent builders. The detergent composition of the invention may also optionally contain one or more types of inorganic detergency builders other than those listed hereinabove which also act as alkalinity sources or chelating agents. Such optional inorganic builders may include, for example, aluminum silicates, such as zeolites. Aluminum silicate zeolites and their use as detergent builders are more fully described in Corkill et al., U.S. Patent No. 4,605,509; issued on August 12, 1986, the disclosure of which is incorporated herein by reference. Also, crystalline layered silicates, such as those discussed in this' 509 U.S. Patent, are suitable for use in the detergent compositions herein. If used, optional inorganic detergency builders may comprise about 2 to 15% by weight of the compositions herein.
• Thickening, viscosity control and / or dispersing agents. The detergent composition of the invention may also optionally contain a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate ingredients in suspension. Thus, such materials may act as thickeners, viscosity control agents and / or dispersants. Such materials are often polymeric polycarboxylates but may include other polymeric materials such as polyvinylpyrrolidone (PVP), carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), poly (vinylpyridine-N-oxide), poly (vinylimidazole), and polymeric amine derivatives. such as quaternized, ethoxylated hexamethylenediamines. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and laurylmethacrylic acid. The presence in the polymeric polycarboxylates herein of monomeric segments containing no carboxylate radicals, such as vinylmethyl ether, styrene, ethylene, etc., is suitable, provided that such segments do not constitute more than about 40% by weight of the polymer. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably in the range of about 2,000 to 10,000, more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers may include, for example, the alkali metal salts. Lösli These polymers are known materials. The use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Dieh-i, U.S. Patent 3,308,067, issued March 7, 1967. Such materials can also perform a builder function. If used, optional thickening, viscosity control and / or dispersing agents should be present in the compositions herein to a level of from about 0.1% to 4% by weight. More preferably, such materials may comprise about 0.5 to 2% by weight of the detergent compositions herein.
• - Optional brighteners, suds suppressants and / or perfumes. The detergent composition of the invention herein may optionally contain conventional brighteners, suds suppressors, silicone oils, bleach catalysts and / or perfume materials. Such brighteners, suds suppressors, silicone oils, bleach catalysts, and perfumes, of course, must be compatible and non-reactive with the other compositional ingredients in the environment of the liquid detergent composition. As used herein, brighteners, suds suppressors and / or perfumes typically comprise from about 0.01% to 5% by weight of the compositions herein. Suitable bleach catalysts include the manganese-based complexes disclosed in U.S. Pat US 5,246,621 . US 5,244,594 . US 5,114,606 and US 5,114,611 , one.
• - Optional organic additives. The detergent composition of the invention may contain an organic additive. A preferred organic additive is hydrogenated castor oil and its derivatives. Hydrogenated castor oil is a commercially available product, for example, in various classes under the trademark CASTORWAX.RTM. from NL Industries, Inc., Highstown, New Jersey. Other suitable hydrogenated castor oil derivatives are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST. A particularly preferred hydrogenated castor oil is thixatrol ST. The castor oil can be added as a mixture, for example, with stereamide. The organic additive is partially dissolved in a non-aqueous liquid diluent. To form the structured liquid phase required for proper phase stability and rheology, the organic additive is generally present at a level of from about 0.05 to about 20 weight percent of the liquid phase. More preferably, the organic additive comprises about 0.1 to 10% by weight of the liquid phase of the detergent composition of the invention.
• Other optional detergent ingredients, such as fabric softeners, including clays, suds boosters, anti-corrosion agents, soil suspending agents, anti-redeposition agents, dyes, bactericides, hydrotropes, and anti-haze agents.

method for the production of liquid Detergent Compositions

The liquid Detergent compositions herein can be prepared by mixing the liquid phase and by subsequent Adding the extra particulate Ingredients in any convenient order to this Phase and by mixing, e.g. Stir, the resulting ingredient combination to form a stable Composition are produced. In a typical procedure for the preparation of such compositions become essential and certain preferred optional ingredients in a particular Order and combined under certain conditions. method for the production of liquid Detergents, including non-aqueous liquid Detergents are well known in the art, and an example is in WO 99/00478, pages 27-32, incorporated herein by reference.

uses

The The invention also relates to the use of a liquid composition of Invention for cleaning an article. The article is preferably a cellulosic tissue.

The The present invention is not limited by the following Examples illustrate:

EXAMPLES

Example 1:

Production of enzyme particles, comprising spray-dried Protease enzyme in a wax of the type PEG 4000.

Spray dried protease enzyme was prepared by conventional drying of a liquid solution of Savinase ^® - prepared, purified by removing non-proteinaceous material, - a protease, available from Novo Nordisk A / S Denmark commercially. The obtained spray-dried powder had the following properties:
Enzyme activity: 89 KNPU / g
Dry matter: 95% by weight
Particle size distribution: 99% by weight <60 microns

180 g of PEG 4000 were transferred to a beaker in a water bath at 80 ° C and held there until it was molten. 20 g of spray dried Savinase ^® were added under stirring and a homogeneous suspension / dispersion was obtained. The suspension was poured onto a table and cooled, which solidified the wax. The solidified melt was broken to give the following particles:
Enzyme activity: 8.0 KNPU / g
Particle size distribution: 250 microns <94% <850 microns
Bulk density: 0.54 g / ml
Actual density: 1.25 g / ml (measured in kerosene)

Example 2:

Production of enzyme particles, comprising spray-dried Protease enzyme in a wax of the type NAFOL 1822:

180 grams of NAFOL 1822 were transferred to a beaker in a water bath at 80 ° C and held until melted. 20 g of spray dried Savinase ^® of Example 1 were added with stirring. The homogeneous suspension was poured onto a table and cooled, which solidified the wax. The solidified melt was broken to give the following particles:
Enzyme activity: 5.1 KNPU / g
Particle size distribution: 250 microns <95% <850 microns
Bulk density: 0.45 g / ml
Actual density: 0.96 g / ml (measured in kerosene)

Example 3:

Production of enzyme particles, comprising spray-dried Protease in waxes of the type PEG 4000 and NAFOL 1822 in combination:

90 grams of PEG 4000 and 90 grams of NAFOL 1822 were transferred to a beaker in a water bath at 80 ° C and held until melted. 20 g of spray dried Savinase ^® of Example 1 was added with stirring. The homogeneous suspension was poured onto a table and cooled, which solidified the wax. The solidified melt was broken to give the following particles:
Bulk density: 0.43 g / ml
Actual density: 1.06 g / ml (measured in kerosene)

As can be observed, show the results obtained in this example the feasibility of combining two different waxes with different ones actual Densities in the process for the preparation of enzyme part chen with a desired actual Density between the actual Densities of individual waxes.

Example 4:

One non-aqueous liquid Detergent comprising enzyme-containing particles is prepared according to the example 1, pages 31-35 in WO 99/00471, except that the "enzyme prills" of WO 99/00471 by the particles of Example 1 or 2 or 3, supra were.

Example 5:

Production of enzyme particles, comprising spray-dried Protease enzyme in wax of the type PEG 4000

18 kg Savinase ^® concentrate were mixed with 3.24 kg Sodium sulfate. The mixture was spray dried by conventional procedures as in Example 1. The spray-dried concentrate contained an enzyme protease activity of 76 KNPU / g.

8.5 kg PEG 4000 was melted and 1.1 kg spray dried Savinase ^® were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 9.4 KNPU / g
Bulk density: 0.69 g / ml
Actual density: 1.11 g / ml (measured in Softanol 50)

Example 6:

Production of enzyme particles, comprising spray-dried Protease enzyme and light beads of the type Expancel (as density modifier) in wax of the type PEG 4000

8.5 kg PEG 4000 was melted and 1.1 kg spray dried Savinase ^® (from Example 5) were added with stirring. 960 grams of Expancel 461DE20 beads were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 8.5 KNPU / g
Bulk density: 0.64 g / ml
Actual density: 1.04 g / ml (measured in Softanol 50)

Compared with example 5 was the actual Density significantly reduced.

Example 7:

Production of enzyme particles, comprising spray-dried Protease enzyme (containing thiosulfate) in wax of the type PEG 4000

Savinase ^® 18 kg concentrate was mixed with 1.62 kg Sodium sulfate and 1.62 kg Sodium thiosulfate (as antioxidant). The mixture was spray dried by conventional procedures as in Example 1. The spray-dried concentrate contained an enzyme protease activity of 71 KNPU / g.

8.5 kg PEG 4000 was melted and 1.1 kg spray dried Savinase ^® were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 8.4 KNPU / g
Bulk density: 0.73 g / ml
Actual density: 1.16 g / ml (measured in Softanol 50)

Example 8:

Production of enzyme particles, comprising spray-dried Protease enzyme (containing thiosulfate) and light beads of the type Expancel (as density modifier) in wax of the type PEG 4000

8.5 kg PEG 4000 was melted and 1.1 kg spray dried Savinase ^® (from Example 7) were added with stirring. 960 grams of Expancel 461DE20 beads were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 9.8 KNPU / g
Bulk density: 0.63 g / ml
Actual density: 1.04 g / ml (measured in Softanol 50)

Compared with example 7 was the actual Density significantly reduced.

Example 9:

Production of enzyme particles, comprising spray-dried Protease enzyme in wax of the type Lutensol AT80

8.5 kg Lutensol AT80 was melted and 1.1 kg spray dried Savinase ^® (from Example 5) were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 9.1 KNPU / g
Bulk density: 0.62 g / ml
Actual density: 1.14 g / ml (measured in Softanol 50)

Example 10:

Production of enzyme particles, comprising spray-dried Protease enzyme and light beads of the type Expancel in wax of the type Lutensol AT80

8.5 kg Lutensol AT80 was melted and 1.1 kg spray dried Savinase ^® (from Example 5) were added with stirring. 960 grams of Expancel 461DE20 beads were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 8.5 KNPU / g
Bulk density: 0.53 g / ml
Actual density: 1.06 g / ml (measured in Softanol 50)

Compared with example 9 was the actual Density significantly reduced.

Example 11:

Production of enzyme particles, comprising spray-dried Amylase enzyme in wax of the type PEG 4000

18 kg Duramyl ^® concentrate were mixed with 2.80 kg of sodium sulfate. The mixture was spray dried by conventional procedures as in Example 1. The spray-dried concentrate contained an enzyme amylase activity of 1650 KNU / g.

6.65 kg PEG 4000 was melted and 0.86 kg spray dried Duramyl ^® were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 115 KNU / g
Actual density: 1.18 g / ml (measured in Softanol 50)

Example 12:

Production of enzyme particles, comprising spray-dried Amylase enzyme and light beads of type Expancel in wax type PEG 4000

5.5 kg PEG 4000 was melted and 1.4 kg spray dried Duramyl ^® (from Example 11) was added with stirring. 115 gram lightweight Expancel 461DE20 beads were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 290 KNU / g
Actual density: 1.01 g / ml (measured in Softanol 50)

Compared with example 11 was the actual one Density significantly reduced, even though the particles significantly more Enzyme powder as in Example 11 contained.

Example 13:

Production of enzyme particles, comprising spray-dried Amylase enzyme and light beads of type Q-CEL in wax type PEG 4000

5.5 kg PEG 4000 was melted and 1.27 kg spray dried Duramyl ^® (from Example 11) was added with stirring. 140 gram light beads of the type Q-CEL-300 were added with stirring. The suspension was spray cooled in a spray cooling tower and the resulting particles were collected and sieved between 250 and 600 microns. This resulted in the following properties:
Activity: 300 KNU / g
Actual density: 1.10 g / ml (measured in Softanol 50)

Compared with example 11 was the actual one Density significantly reduced, even though the particles significantly more Enzyme powder as in Example 11 contained. Nevertheless, Q-CEL 300 is less efficient while reducing the actual Density as Expancel used in Example 12.

Example 14:

A nonaqueous liquid detergent matrix was prepared according to the guidelines set forth in patent application WO 99/00478, Example 1, without the addition of driers:
150 g of diethylene glycol monobutyl ether
150 g Synperonic A7 (a POE (7) synthetic C ₁₃ / C ₁₅ primary alcohol from ICI)
were mixed at 45 ° C for 5 minutes
150 g of dodecylbenzene sulfonic acid Na salt (LAS)
was added and the mixture was stirred for a period of 30 minutes.

0.5 g of enzyme particles were added to 4 g of detergent matrix. The visual Appearance of the particles after 24 hours storage at room temperature was checked:

All tested enzyme particles showed good physical stability in the Detergent matrix.

Claims (65)

A substantially non-aqueous liquid detergent composition comprising a surfactant and solid particles dispersed in the liquid phase, the solid particles comprising a solid wax matrix in which an active agent, preferably in solid particulate form, is distributed, the particles having an actual density between about plus 0.5 g / cm ³ to about minus 0.5 g / cm ^{3 of} the actual density of the liquid phase, and wherein the wax is water-soluble or water-dispersible. The liquid composition of claim 1, wherein the wax has an actual density between about plus 0.5 g / cm ³ to about minus 0.5 g / cm ^{3 of} the actual density of the liquid phase. liquid A composition according to any one of the preceding claims, wherein the wax is insoluble in a substantially non-aqueous liquid or is undispersible. liquid A composition according to any one of the preceding claims, wherein the wax has a melting point or range between about 35 ° C to about 120 ° C has. liquid Composition according to one of the preceding claims, wherein the wax is selected from the group consisting of polyethylene glycols, polypropylenes, Polyethylenes, nonionic surfactant waxes, ethylene oxide, propylene oxide or copolymers thereof, carnauba wax, candelilla wax, beeswax, Hydrogenated Ochsentalg, hydrogenated palm oil, hydrogenated cottonseed, hydrogenated soybean oil, fatty acid alcohols, Monoglycerides, diglycerides, fatty acids and paraffins. liquid A composition according to claim 5, wherein the polyethylene glycol is selected from the group consisting of PEG 1500, PEG 3000, PEG 4000, PEG 6000 and PEG 9000. liquid A composition according to claim 5, wherein the nonionic surfactants is an ethoxylated fatty alcohol. liquid A composition according to any one of the preceding claims, wherein the solid wax matrix comprises a mixture of at least two waxes. liquid A composition according to any one of the preceding claims, wherein the amount of wax at least 35% w / w of an uncoated enzyme-containing Particle forms. liquid A composition according to any one of the preceding claims, wherein a density modifier is distributed in the wax matrix. The liquid composition of claim 10, wherein the density modifier has an actual density that is at least 0.2 g / cm ³ below the actual density of the solid wax matrix incorporating the enzyme. liquid A composition according to claim 11, wherein the density modifier selected is from the group consisting of polysaccharides, light globules and gases. liquid A composition according to claim 12, wherein the gas is atmospheric air is. liquid A composition according to claim 13, wherein the air is in particles in Form of air bubbles distributed in the solid wax matrix is present. liquid The composition of claim 12, wherein the light bead selected is made of solid, hollow, spherical Particles and foamed solid materials. liquid A composition according to claim 15, wherein the foamed solid Material is polystyrene. liquid A composition according to claim 15, wherein the solid, hollow, spherical particles made of glass, ceramics and plastic. liquid A composition according to claim 12, wherein the density modifier selected is made of gases and light globules and forms more than 5% w / w of the particle. The liquid composition of claim 10, wherein the density modifier has an actual density that is at least 0.2 g / cm ³ above the true density of the solid wax matrix incorporating the enzyme. liquid A composition according to claim 19, wherein the density modifier selected is from the group consisting of water-soluble or -insoluble inorganic salts, clays, bentonites, talcs, zeolites and silicates. liquid A composition according to claim 20, wherein the inorganic salt is alkali sulfate is. liquid The composition of claim 20, wherein the clay is kaolin. liquid A composition according to any one of the preceding claims, wherein the particle further comprises one or more compounds selected from Stabilizing or protective agents, fiber materials, activators or cofactors, dispersants, viscosity modifiers, fillers and pigments. liquid A composition according to any one of the preceding claims, wherein the particles further comprise one or more coating layers to cover the wax matrix. liquid The composition of claim 24, wherein the coating is a wax includes. liquid A composition according to any one of the preceding claims, wherein the active ingredient is an enzyme. liquid A composition according to any one of the preceding claims, wherein the enzyme is selected is from the group consisting of oxidoreductases (EC 1.-.-.-), Transferases (EC 2.-.-.-), hydrolases (EC 3.-.-), lyases (EC 4.-.-.-), Isomerases (EC 5.-.-.-) and ligases (EC 6.-.-.-). liquid The composition of claim 27, wherein the oxidoreductase is selected from the group consisting of peroxidases (EC 1.11.1), laccases (EC 1.10.3.2) and glucose oxidases (EC 1.1.3.4)]. liquid The composition of claim 27, wherein the hydrolase is selected from the group consisting of amylase, protease, lipase and mannanase. liquid A detergent composition according to claim 27, further comprising one or more ingredients selected from non-aqueous liquid Diluents, EDDS, chelating agents, enzyme stabilizers, bleaching, bleach activators, builders and alkalinity source compounds. A process for preparing a substantially non-aqueous liquid detergent composition according to claim 1, comprising the step of dispersing solid particles in a liquid phase, the particles comprising a solid wax matrix in which an active agent is distributed and an actual density between about plus 0.5 g / cm ³ to about minus 0.5 g / cm ^{3 of} the actual density of the liquid phase and wherein the wax is water-soluble or water-dispersible. Enzyme-containing particle comprising a solid wax matrix from a mixture of at least two water-soluble solid waxes, in which preferably distributes an active substance in solid particle form is. Enzyme-containing particle comprising a solid wax matrix, wherein an active ingredient is preferably in solid particulate form and a Density modifier are distributed in the wax matrix and wherein the wax is water-soluble or water dispersible. The enzyme-containing particle of claims 32-33, wherein the wax is insoluble in a substantially non-aqueous liquid or is undispersible. The enzyme-containing particle of claims 32-34, wherein the wax has a melting point or range between about 35 ° C to about 120 ° C has. Particles according to claims 32-35, wherein the amount of wax is at least 35% w / w of the particle. Particles according to claim 33, wherein the wax is selected from the group consisting of polyethylene glycols, polypropylenes, Polyethylenes, nonionic Surfactant waxes, ethylene oxide, propylene oxide or copolymers thereof, Carnauba Wax, Candelilla Wax, Beeswax, Hydrogenated Ochsentalg, hydrogenated palm oil, hydrogenated cottonseed, hydrogenated soybean oil, fatty acid alcohols, monoglycerides, Diglycerides, fatty acids and paraffins. Particles according to claims 32-37, wherein the polyethylene glycol selected is from the group consisting of PEG 1500, PEG 3000, PEG 4000, PEG 6000 and PEG 9000. Particles according to claims 32-37, wherein the nonionic surfactants are ethoxylated fatty alcohols. The particle of claim 32, further comprising a density modifier. Particles according to claim 33 or 40, wherein the density modifier has an actual density which is at least 0.2 g / cm ³ below the actual density of the solid wax matrix incorporating the enzyme. Particles according to claim 41, wherein the density modifier selected is from the group consisting of polysaccharides, light globules and gases. Particles according to claim 42, wherein the gas is atmospheric air is. Particles according to claim 43, wherein the air in the particle in the form of air bubbles distributed in the solid wax matrix. Particles according to claim 42, wherein the light bead selected is made of solid, hollow, spherical Particles and foamed solid materials. Particles according to claim 45, wherein the foamed solid Material is polystyrene. Particles according to claim 45, wherein the solid, hollow, spherical Particles made of glass, ceramics and plastic are made. Particles according to claim 42, wherein the density modifier selected is made of gases and light globules and forms more than 5% w / w of the particle. Particles according to claim 33 or 40, wherein the density modifier has an actual density which is at least 0.2 g / cm ³ above the actual density of the solid wax matrix incorporating the enzyme. Particles according to claim 49, wherein the density modifier selected is from the group consisting of water-soluble or -insoluble inorganic salts, clays, bentonites, talcs, zeolites and silicates. Particles according to claim 50, wherein the inorganic Salt is alkali metal sulfate. Particles according to claim 50, wherein the clay is kaolin is. Particles according to claim 32-52, wherein the particle of the Further one or more compounds distributed therein selected from Stabilizing or protective agents, fiber materials, activators or cofactors, dispersants, viscosity modifiers, fillers and pigments. Particles according to claims 32-53, wherein the active ingredient is a Enzyme is. Particles according to claim 54, wherein the enzyme is selected from the group consisting of oxidoreductases (EC 1.-.-.-), transferases (EC 2.-.-.-), hydrolases (EC 3.-.-.-), lyases (EC 4.-.-.-), isomerases (EC 5.-.-.-) and ligases (EC 6.-.-.-). Particles according to claim 55, wherein the oxidoreductase selected is from the group consisting of peroxidases (EC 1.11.1), laccases (EC 1.10.3.2) and glucose oxidases (EC 1.1.3.4)]. Particles according to claim 55, wherein the hydrolase is selected from the group consisting of amylase, protease, lipase and mannanase. Particles according to claims 32-57, wherein the particle of the Further, one or more coating layers around the wax matrix includes. Particles according to claim 58, wherein the coating includes a wax. A process for producing a particle comprising one in a water-soluble one or water-dispersible wax matrix distributed drug comprising the steps: (a) preparing a mixture I comprising first wax preferably in molten form and a density modifier, or (b) preparing a mixture II comprising a first Wax preferably in molten form and one or more additional Preferably waxes in molten form with a lower one or higher density as the first wax and a density modifier, (C) Disperse or dissolve an active substance in mixtures I or II, (d) manufacture of active substance-containing particles by solidifying in step (c) the resulting dispersion or solution. The method of claim 60, comprising step (a). The method of claim 60, comprising step (b). The method of claim 60, wherein step (d) is the following step includes: (a) atomizing the dispersion or solution in droplet and (b) solidifying the droplets to solid particles by cooling of an object. Use of the liquid detergent according to claim 1-30 to Cleaning an item. Use according to claim 64, wherein the article a cellulosic substance.