MXPA98010048A - New granulated enzyme materials comprising an enzyme and a nucleus of organic disulfide - Google Patents

Abstract

The present invention discloses novel granulated enzyme materials containing an organic disulfide compound (R1-S-S-R2), particularly containing the free amino acid cystine, optionally mixed with the amino acid cystine. The new granulated enzyme materials are for use in detergent and cleaning compositions, particularly in dishwashing compositions, and have positive properties, for example in respect to protecting objects made of silver or coated with silver against staining for example, dishes, cutlery and other objects that are going to be cleaned

Description

NEW GRANULATED ENZYME MATERIALS THAT COMPRISE AN ENZYME AND AN ORGANIC DISULFIDE NUCLEUS DESCRIPTION OF THE INVENTION The present invention relates to new granulated materials of enzymes containing an organic disulfide compound, to a method for the production of the new granulated enzyme materials, as well as to its use in detergent, cleaning and bleaching compositions. and for dishwashers. In many detergent and cleaning compositions, for example, for cleaning textiles or dishes, enzymes are used to increase detergent or cleaning effectiveness. Usually the enzymes used are proteases-> , lipases, amylases or celluloses; the enzymes can here be used as individual enzymes or as mixtures of enzymes. The enzymes are added to pulverizing or granular detergent and cleaning formulations in the form of the so-called granulated enzyme materials, which contain the enzyme or mixture of enzyme in question together with a filler, binder, and optionally additional granulation and formulation aids. Such granulated enzyme materials are usually REF: 28881 prepared by processing an enzyme concentrate with filler and binder, and optionally additional granulation and formulation aids to form a composition which is then granulated. The resulting wet granulated material particles are, if desired, more rounded, and then dried. Optionally the dried granulated particles are then coated with a protective lacquer, and then they can be used in detergent and powdered or granulated cleaning formulations. The problem therefore consisted in making available new granulated materials of enzymes containing, in addition to the usual granular components, a further formulation component which has an advantageous effect on the properties of the granulated material of enzyme itself and also in the application of the formulations; The granulated enzyme materials prepared should be particularly suitable for use in pulverized or granular detergent and cleanser formulations, preferably in dishwashing formulations. Enzyme granule materials having the required properties, and which are indicated in claims 1-12, have now been discovered. The object of the invention is therefore a granulated enzyme material consisting of a core, which contains at least one enzyme and, in addition, fillers, binders, humectants, water-soluble and / or water-insoluble as well as optionally, additional granulation or formulation aids and, optionally, enzyme stabilizing agents, and optionally, one or more protective layers surrounding the core. Wherein the granulated enzyme material is characterized in that the core contains an organic disulfide compound (R? -S-S-R2), preferably the free amino acid cystine, which may optionally be in the form of a cystine / cysteine mixture. An advantageous granulated material of enzyme of the invention is characterized in that the content of organic disulfide compound in the core, preferably the amino acid cysteine, is up to 20% by weight with respect to the granulated enzyme material as 100% by weight (dry weight without humidity) . Preferably, the content of organic disulfide compound, in the granulated enzyme material in the core, particularly the amino acid cysteine, is up to 15% by weight with respect to the granulated material of 'enzyme as 100% by weight (dry weight without moisture ).

In a granulated material of advantageous enzyme according to the invention, the core has in particular the following composition, with respect to the granulated enzyme material as 100% by weight (dry weight without moisture): 0.8-20% by weight of enzyme or mixture of enzyme (enzyme protein content) 40-90% by weight of water-soluble and / or water-insoluble fillers, 5-15% by weight of binders, 0.2-5% by weight of humectants, 3-20% by weight of organic disulfide compound, preferably the amino acid cysteine, and optionally, up to 10% by weight of granulation aids or formulation additional standards and optionally, up to 5% by weight of enzyme stabilizing agents. In a preferred embodiment of the enzyme granulated material according to the invention, the core has a content, with respect to the granulated enzyme material as 100% by weight (dry weight without moisture) of 1-10% by weight of enzyme or mixture of enzyme (content of enzyme protein) 60-85% by weight of water-soluble and / or insoluble fillers in water, 10-15% by weight of binders, 0.2-2% by weight of humectants, 5-15% by weight of organic disulfide compound, preferably the amino acid cystine, and optionally, up to 10% by weight of additional standard granulation or formulation aids, and optionally, up to 5% by weight of enzyme stabilizing agents. The granulated enzyme materials according to the invention are characterized by their advantageous content of the organic disulfide compound R? -S-S-R2. The disulfide group -SS- can here carry the organic residues Ri and R2, where these residues, particularly alkyl residues, can be identical or different or can be combined with the disulfide group -SS- to form a ring, and wherein, optionally, these residues, particularly alkyl residues, may also be substituted by amino groups, carboxy groups (in acid form or in salt form, particularly with alkali metals) or hydroxy groups. Examples of residues Ri and R2 are, for example, the 2-hydroxyethyl residue, the l-carboxy-2-hydroxy-2-yl residue and the l-carboxy-2-aminopropan-3-yl residue, and Ri and Rr / together R1-SS-R2 as a ring, the residue 2, 3-butanediol-l, 4-diyl. Suitable organic disulfide compounds are thus, for example, 2,2'-dithiodiethanol, 2,2-r -dithiodiglycolic acid and, in particular, 3,3'-dithiobis (2-aminopropionic acid), also to the amino acid cysteine, as well as also the cyclic disulfide of 1,4-dimercapto-2,3-butanediol (dithiothriethol, dithioerythritol), wherein the cyclic dimer may optionally also be in the form of a mixture with the open dimer and / or the monomer for 1, 4 -dimercapto-2, 3-butanediol. The content of the preferred amino acid cysteine in the present may also be in the form of a cystine / cysteine mixture, because the cysteine (HS-CH2-CH (NH2) -COOH acid, 2-amino-3-mercaptopropionic acid) is oxidized easily to cystine in an aqueous neutral or alkaline solution. The ratio by weight of cystine to cysteine in the present can vary in this variant of the invention in a wide range, in particular, within the context of the invention, in the range from 90: 1 to 1: 1. The above weight ratio is applied, by analogy, to mixtures of the cyclic disulfide of 1,4-dimercapto-2,3-butanediol with the open dimer or the monomer. The granulated enzyme material according to the invention may contain water-insoluble or water-soluble fillers, which by themselves are standard, either alone or in the usual mixtures of one with the other. The water-insoluble filler is selected in particular from the group of cellulose, zeolite or silicate, for example layered silicate, grain meal, vegetable meal or malvaceae and / or starch.

The mixture of water insoluble fillers contained in the advantageous enzyme granulated materials according to the invention consists of a mixture of cellulose and at least one zeolite or silicate, particularly layered silicate, wherein, in a preferred embodiment, the flour of Grain and / or starch optionally constitute additional components of the mixture of water insoluble fillers. The grain flour and the starch may in the present be used either alone or as a mixture with one another. As grain meal it is possible to use any of the flours which by themselves are known, made from wheat, rye, barley, oats, rice or corn. It is preferred to use wheat flour. In a further preferred variant of the invention, legume flours or malvaceae are used as water-insoluble fillers or as components of the water-insoluble filler blends. The source of the flour for this variant of the invention consists of legume fruits. The legumes are defined as food plants (pods) that belong to the plant fruits. Therefore, sources for legume flours include the fruit of legume species such as Pisu (peas), Caja us (pigeon peas), Cicer (chickpeas), Lens (lentils); Phaseolus (beans), Vigna (cowpea), beans of Dolchius Chyacinth, Cassavalia beans of canavalia, Vicia (horse bean or peas); Peluschken (unknown translation); Arachis (peanuts); lupins; alfalfa; soybeans as well as beans and optionally other pods and also fruits of malvaceae (for example, the genus Gossipiu, cotton). It is particularly preferred to use the peas and particularly the soy beans. The vegetable flours or the flours made from the fruit of the family Alavaceae are particularly advantageous as the auxiliary for the production of granulated materials of the enzyme according to the invention, because when they are used as carriers and fillers, and also when they are used as Additional formulation components in addition to other standard carriers and fillers, develop a positive effect on the enzyme stability of both, the individual enzymes and also the enzyme mixtures, and on the powder properties of the granulated enzyme materials prepared with the same; additionally, these flours allow a simpler one, considered with enzymes and, compared to other standard carriers or fillers, a more economical production of granulated enzyme materials. For the preparation of the legume flour or malvaceae it is possible to use, among the oil-containing fruit of the examples mentioned above, fruits of which all the oil has been removed, some of the oil has been eliminated, as well as fruit that contains oil; for this purpose it is preferred to use fruit from which a part of all the oil has been removed, particularly, fruits of vegetables of which a part of the oil or all the oil has been eliminated, for example, soybean which has largely been released from its oil content. The removal of the oil can be carried out herein in a manner that is itself standard. Preferred for the material is the enzyme granulate which contains, as a water-insoluble filler, a mixture of cellulose, at least one zeolite or silicate, particularly a layered silicate, and optionally at least one grain meal and / or or legume flour or malvaceae. The cellulose component in the mixture of water-insoluble fillers consists of fibrous cellulose, for example fibrous cellulose in the range of 20-50 μm. Especially preferred is fibrous cellulose with an average fiber length of about 30 μm, which has proven to be suitable. As additional components, the mixture of water insoluble fillers contains zeolites or silicates, particularly layered silicates such as bentonite or kaolin or silicate mixtures in kaolin and bentonite layers. The kaolin may optionally also be in a mixture with calcium carbonate and / or bentonite. The water-soluble filler in the granulated enzyme material according to the invention can be an alkali metal chloride, an alkali metal acetate, an alkali metal sulfate, a calcium carbonate, a sugar such as for example lactose, or a mixture thereof. Optionally sugars are used as the water soluble fillers in the granulated enzyme materials according to the invention, then it is advantageous to use monosaccharides such as glucose or disaccharides such as lactose and / or maltose or polysaccharides such as dextrin. Mixtures of sugars such as, for example, glucose syrup are also suitable. It is preferred to use disaccharides, particularly lactose and / or maltose as the sugar component in the filler in the granulated enzyme materials according to the invention. Advantageously, the sugars mentioned above are used in the granulated enzyme materials according to the invention in an amount of 0.5-10% by weight, particularly 1.0-5.0% by weight, with respect to the total solids content of the granulated enzyme material . As mixtures of water-soluble fillers it is advantageous to use inorganic water-soluble salts such as, for example, alkali metal chlorides, alkali metal acetates, alkali metal sulfates or mixtures thereof in the granulated enzyme material according to the invention. invention. It is preferred to use alkali metal sulfates, particularly sodium sulfate. The granulated enzyme material according to the invention may also contain binders or binder mixtures which by themselves are standard. Preferred for the granulated enzyme material of the invention which contains as a binder, polyethylene glycol with molecular weights in the range 200-10,000 a polyvinylpyrrolidone with molecular weights in the range of 12,000-3,000,000, wheat starch and / or gluten; if polyvinylpyrrolidone is used as the binder, its preferred molecular weights are in the range of 1,300,000-2,800,000. The binders can be used either alone or in combination with one another. One embodiment of the granulated enzyme material according to the invention contains, with respect to the granulated finished enzyme material (such as 100% by weight, dry weight), at least 0.2% by weight of a humectant. As a humectant it is possible to consider using surfactants which by themselves are standard and tolerant of the enzymes, optionally also in combination, particularly non-ionic surfactants and mild ionic surfactants. In an advantageous embodiment of the invention, the humectant is a non-ionic surfactant from the group of alcohols ethoxylated with 5-85 ethoxy groups for example, dodecylethoxylated alcohol with 80 ethoxy groups, or a surfactant from the group of esters of sulfosuccinic acid. The amount of the humectant or the combination of humectants should not exceed 5% by weight of granulated enzyme material. Advantageously granulated enzyme materials in particular have a humectant content of 0.2-3% by weight, preferably 0.2-2% by weight. The enzymes in the granulated enzyme material may be the usual enzymes that are known per se and used for detergent and cleansing applications, either alone or in a compatible combination with one another. For the granulated enzyme materials according to the invention, it is thus possible to use any of the standard enzymes for detergent and cleansing compositions, such as for example, proteases, lipases, amylases, glucanases such as, for example, celluloses, hemicelluloses, pullulanases , or oxidoreductases, and lysozyme. The enzymes may be contained in the granulated enzyme materials according to the invention alone or as mixtures of enzymes, for example as protease / amylase mixtures or protease / lipase mixtures. The advantageous enzyme granulated materials of the invention contain, as enzymes, a protease, amylase, cellulase, hemicellulase, lipase, oxidoreductase, lysazyme or any mixture thereof. Commercial examples include Optitherm ™ (thermostable α-amylase), Optimasa ™ (alkaline protease of the BPN 'type [unknown expansion]) Opticlean ™ (highly alkaline protease of the subtilisin 309 type) from the company Solvay Enzymes GmbH & CO. KG (Nienburg, DE). In the context of the present invention it is also possible to use enzymes that have already been altered by genetic engineering, for example, optimized by mutation. In a preferred embodiment, the granulated enzyme materials according to the invention contain a thermostable α-amylase and / or an alkaline or highly alkaline protease. In this context it is particularly advantageous to use proteases for their incorporation into granulated enzyme materials according to the invention having improved properties due to chemical and / or genetic engineering modifications, such as increased detergent efficiency or increased stability. Here the so-called subtilisins are particularly advantageous as alkaline proteases. Subtilisins are alkaline proteases with an optimum pH in the alkaline pH range and an essential serine residue in the active center. They can be extracted, in a way that is itself known, from Gram positive bacteria or fungi. Here it is preferred to use subtilisins extracted from Bacillus strains, for example subtilisins such as subtilisin BPN ', subtilisin from Carlsberg and subtilisins which can be isolated from Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus lentus, Bacillus mesentericus or Bacillus alkalophilus. It was particularly preferred to use subtilisins having an optimum pH in the range of 7-13, and which are commercially available, for example, as Savinase ™, MaxacalRM, Durazym ™, Maxapen or OpticleanRM. Enzymes that are suitable for the granulated enzyme materials according to the invention can be obtained, in a way that in itself is known, by fermentation process of appropriate microorganisms, particularly bacteria or fungi. The fermentation broths obtained in the fermentation are liberated from insoluble accompanying substances, for example by filtration, and then are reduced in a manner that is itself known, for example, using membrane filtration processes such as micro- and / or ultrafiltration with optionally, subsequent dialysis and / or thin layer evaporation. In this way the so-called enzyme concentrates are obtained, which usually contain the enzyme or enzyme mixtures in an amount of 2-50% by weight with respect to the dry substance, in addition to possibly other accompanying substances that have not been separated. . If desired, these liquid enzyme concentrates can be further transformed, for example, by spray drying and / or lyophilization, into dry enzyme concentrate. The granulated enzyme materials according to the invention can, in each case with respect to the total solids content, have, for example, a composition which is such that the water-insoluble filler mixture consists of 15-40% by weight of cellulose , 5-18% by weight of kaolin, if desired in a mixture with 1-35% by weight of bentonite and 1-13% by weight of calcium carbonate. Optionally, it is possible to use, as additional insoluble water-based fillers, 0-50% by weight of grain meal and / or legume meal and / or 0-50% by weight of starch. Usually 0.5-20% by weight of sodium sulfate is used as a water soluble filler. In addition, up to 30% by weight of binder of the polyethylene glycol group and the polyvinylpyrrolidone can be used in the content. The enzyme can be incorporated as an enzyme concentrate in an amount of up to 40% by weight in the granulated enzyme materials according to the invention. To stabilize the enzymes, the granulated materials may contain 0.5-15% by weight of alkali metal formate or alkaline metal formate and optionally, 0.5-20% by weight of sugar, in particular reducing disaccharides such as lactose, as it was described above as a water soluble filler. In an advantageous embodiment, a granulated enzyme material according to the invention contains, the core, in each case with respect to the content of total solids (without moisture content), of 0.8-20% by weight of enzyme or mixtures of enzymes (enzyme protein), 4-26% by weight of cellulose, 5-25% by weight of grain meal and / or pulse meal, optionally 0-20% by weight of starch, 0-20 % by weight of kaolin, 0-10% by weight of calcium carbonate, 0-10% by weight of sodium sulfate, 5-15% by weight of polyethylene glycol (molecular weight 3,000), from 1-5% by weight of lactose, 6-20% by weight of bentonite, 0.2-5% by weight of humectant and a total of 3-20% by weight of the organic disulfide compound, preferably cystine or a mixture of cystine / cysteine. Naturally, the granulated enzyme materials according to the invention can contain, in addition to the above-mentioned principal components, additional granulation auxiliaries such as, for example, lubricants or dispersants. Possible lubricants that can be used include a glycerol monoester with large chain fatty acids and an example of a dispersant is an ester of sulfosuccinic acid with large chain fatty alcohols in concentrations of up to 10% by weight. In addition, the invention comprises a method for the production of granulated enzyme materials, in which a mass can be extruded which was prepared by mixing an enzyme preparation with water, fillers, binders and optionally additional components, can be extruded to particles, followed by rounded off the particles produced in an apparatus for rounded, subsequent drying of the rounded particles and optionally, coating the particles with a protective layer, with addition to the dough to be extruded from the organic disulfide compound, preferably the amino acid cystine or a mixture of cystine / cysteine, in an amount of up to 20% by weight, particularly in an amount of 0.5-20% by weight, with with respect to the total solid matter content of the granulated enzyme material. In the method according to the invention, it is possible to use liquid enzyme concentrates as enzyme preparations, wherein the enzyme concentrates are prepared in a manner that is itself known by the fermentation of microorganisms and the processing of the fermentation broth. produced by fermentation. In the sense of the invention, the enzyme preparations are defined to include solid concentrates from above which can be prepared, for example, lyophilizing liquid enzyme concentrates. Advantageously, the method is carried out in such a way that the enzyme concentrate is added to a dry premix previously prepared from the components of the recipe or powdered formula remaining in a suitable mixing apparatus, for example, a conical mixer or a grate mixer. Then water is added in an amount that is dosed in such a way that a mass is formed which is easily formed and extruded. Usually the moisture content of this mixture is 20-50% by weight. The extrudable mixture obtained in this way is mixed in the mixer until homogeneous, and then brought to the extruder. In the extruder the mass is extruded by means of a perforated disk having a perforation diameter of 0.4-3 mm, preferably of 0.6 mm, to form filaments, which are then rounded in an apparatus for rounding, for example, a disk apparatus rotary, to spherical particles, after rounding of the particles, which are still wet, are dried in a drying such as, for example, a fluidized bed dryer, at a temperature of 30-50 ° C up to a residual moisture content of 10-2% by weight. If desired, the obtained granulated enzyme materials can be coated during and / or after this process step with a protective lacquer, to thereby protect the particles of granulated enzyme material from external influences, for example, or to cover any color that the particle can have by itself, or to change the color of the particle. To obtain granulated enzyme materials with a light color, the granulated enzyme materials can be coated, for example, with a dispersion containing titanium dioxide in a manner that is itself known. For this purpose it is possible to disperse titanium dioxide with polyethylene glycol as a binder in water in a known manner, and to inject it through nozzles to the drying facility. According to the method of the invention, granulated enzyme materials are obtained consisting, to a high degree, of dust-free rounded particles having a diameter of 0.2-1.0 mm and a density of 600-1,100 g / 1, and which is advantageously suitable as components of powdered or granular detergents and cleaners. Another object of the invention consists of the use of the granulated enzyme materials according to the invention in pulverized or granular detergents or cleaners, bleaching or dishwashing formulations, advantageously in dishwashing formulations containing bleaching agents. Such detergents and cleaners can, for example, be used for cleaning surfaces, for example, to remove grease residues in the hygiene or food sectors. The granulated enzyme materials according to the invention are preferably used in detergent and cleaning formulations for cleaning textiles or tableware. In addition to the granulated enzyme materials, the detergent and cleaning formulations herein may contain all the standard detergent components used in the current state of the art., such as surfactants, bleaches or additives, as well as other standard auxiliaries for the formulation of powdered detergents and cleaners, in amounts that are themselves standard. Auxiliaries include, for example, reinforcing agents, enzyme stabilizing agents, dirt carriers and / or compatibilizing agents, complexing agents and chelating agents, foam regulators and additives such as optical brighteners, opacifying agents, inhibitors. of corrosion, antielectrostatic agents, dyes, bactericides, bleaches, activators, peracid bleach precursors. They may contain, in addition to the granulated enzyme materials according to the invention, bleaches or mixtures of bleach based on peracid compounds, for example, perborate, such as sodium perborate tetrahydrate, sodium perborate monohydrate or sodium percarbonate. , in quantities that in themselves are standard in detergent or dishwashing compositions. By the incorporation of the organic disulfide compound, particularly cystine or the cystine / cysteine mixture, in the granulated material according to the invention, the enzymes are stabilized, particularly the α-amylase or the so-called proteases, in a surprising manner. Thus, the granulated enzyme materials according to the invention have very good properties, which are particularly well suited to use powdered detergent and cleanser formulations. In the sprayed formulations, particularly in the bleach-containing formulations or in the oxidant formulations, they exhibit good storage stability, and consequently they are particularly well suited for formulations containing oxidation agents as well, such as, for example, peroxide-containing formulations . Because the granulated enzyme materials according to the invention prevent a markedly low powder and an enzyme powder content, they have a very good processability. A further advantage is that large losses of enzyme can be avoided during the production of the granulated enzyme materials according to the invention. In addition, the granulated enzyme materials according to the invention exhibit excellent dissolution properties during the washing or cleaning process. Thus, already within two minutes, more than 90% of the enzyme is released from the granulated enzyme materials according to the invention within the detergent solution, so that during the washing or cleaning process, a very long action time Prolonged enzyme on the corresponding cleaning object, eg tableware or cutlery, is guaranteed. Furthermore, the granulated enzyme materials according to the invention, in dishwashing machine compositions, have a particularly good effect in protecting objects made of silver or silver-coated objects for example, tableware, cutlery and other objects to be cleaned. of fogged or stained, on account of its content of organic disulfide compound, particularly cystine or a cystine / cysteine mixture. The following examples should further explain the invention, without, however, limiting its scope.

Examples Example 1: Production of a granulated enzyme material with thermostable α-amylase The components of the formula listed in the example formulas set forth below are mixed in a Lodige type rapid mixer together with the liquid enzyme concentrate to form a mass that can be extruded The extrusion is carried out in a twin-screw extruder of the Fuji-Paudal EXDCS60 type through a perforated metal sheet with a perforation diameter of 600 μm. The extruded material was then rounded in a Fuji-Paudal Q400 type Marumizer and then dried in a fluidized bed dryer of the Glatt GPCG5 type at marumes ca[translation not confirmed]. The lacquer coating of the brown marumes with a lacquer containing pigment was carried out in a fluidized bed coating apparatus of the Glatt GPCG3 type.

Formula of granulated material not coated with lacquer L-cystine USP manufactured by the company Freedom Chemical Diamalt GmbH was used, with the following particle size distribution: The liquid enzyme concentrate used consisted of the following components: 4% by weight of enzyme protein (thermostable α-amylase, activity 840,000 MU / g), 40% by weight of the accompanying substances determined in standard production, 1% by weight of standard preservatives, and 55% by weight of water; pH 6.0. MWU = modified ohlgegmuth unit; what is measured is the amount of enzyme that degrades, under the test conditions, 1 mg of soluble starch within 30 min to a dextrin of defined size.

Formula of granulated materials The formulas of the granulated material (without enzyme) have the following composition (indications in part by weight): Coating formula: For coating, a lacquer having the following formula was used: Water 550 1 PEG 4000 87.5 kg PEG 200 10 1 Calcium carbonate 100 kg Titanium dioxide 200 kg PEG = Polyethylene glycol Results: The finished granulated material had following properties: I g of granulated material in 200 ml of buffer solution (pH 5.4); Temperature 25 ° C.

The enzyme concentrate, and as much water as the pulverized premix required in the conical mixer to produce a mass that can be homogeneously extruded were added. The moisture content of this wet mixture was approximately 30% by weight. The homogeneous wet mixture obtained was transferred to an extruder. Through a perforated matrix with perforation diameters of approximately 0.6 mm, the mass was extruded into filaments. The section of broken filaments obtained was transferred to a rotary disk apparatus, where they were formed into round particles during a processing time of approximately 20 sec. The rounded particles were then dried in a fluidized bed dryer at a temperature of about 48 ° C to a water content of about 5% by weight. The granulated material obtained consisted of rounded particles with diameters of 0.2-1.0 mm. The granulated material was non-adhesive, and was easily emptied with a bulk density of approximately 800 g / 1. Additional properties are indicated in the following table. *) 1 g of granulated material in 200 ml of buffer solution (pH 5.4); temperature 25 ° C. Good processability (ability to be extruded and ability to be formed) of the standard samples was not adversely affected. The solubility was not affected in the case of the use of Opticleare as a cystine protease and, you found, if Optimasa was used as the protease, the solubility was improved. Any reference to the activities of the enzymes in the present application refers to the determinations of activity for the given enzyme which are based on standard methods known per se and familiar to those skilled in the art.

It is noted that in relation to this date, the best method known by the applicant to carry out the present invention, is the conventional one for the manufacture of the objects or products to which it refers. Having described the invention as above, the content of the following is claimed as property:

Claims (14)

1. An enzyme granulated material characterized in that it comprises: a core containing at least one enzyme, water-soluble and / or water-insoluble fillers, binders, humectants or other formulation aids and optionally an enzyme stabilizing agent and optionally one or more layers shields surrounding the core, wherein the core contains an organic disulfide compound (R1-SS-R2), preferably the free amino acid cystine, which may optionally be in the form of a cystine / cysteine mixture.

2. A granulated enzyme material according to claim 1, characterized in that the content of organic disulfide compound in the core, preferably the amino acid cystine, is up to 20% by weight with respect to the granulated enzyme material as 100% by weight (dry weight without moisture).

3. An enzyme granulated material according to claim 2, characterized in that the content of organic disulfide compound in the core, preferably the amino acid cystine, is up to 15% by weight with respect to the granulated enzyme material as 100% by weight .

4. An enzyme granulated material according to claim 2, characterized in that the core, with respect to the granulated enzyme material as 100% by weight (dry weight without moisture), has the composition of 0.8-20% by weight of enzyme or enzyme mixture (enzyme protein content), 40-90% by weight of water-soluble and / or water-insoluble fillers, 5-15% by weight of binder (s), 0.2-5% by weight of humectant (s), and 3-20% by weight of the organic disulfide compound, preferably the amino acid cystine, as well as, optionally, up to 10% by weight of additional additional formulation aids and optionally, up to 5% by weight of stabilizing agents of enzyme.

5. A granulated enzyme material according to claim 3, characterized in that the core, with respect to the granulated enzyme material as 100% by weight (dry weight without moisture), preferably has the following composition: 1-10% by weight of enzyme mixtures (enzyme protein content) 60-85% by weight of water-soluble and / or insoluble fillers in water, 10-15% by weight of binders, 0.2-2% by weight of humectants, and 5- 15% by weight of the organic disulfide compound, preferably the amino acid cystine as well as optionally, up to 10% by weight of additional standard granulation or formulation aids, and optionally, up to 5% by weight of enzyme stabilizing agents.

6. A granulated enzyme material according to any of claims 1-5, characterized in that the content of the amino acid cystine is in the form of a cystine / cysteine mixture.

7. A granulated enzyme material according to claim 1, characterized in that the water-insoluble filler is selected from the group of cellulose, zeolites or silicates, particularly layered silicates, grain flour, vegetable flour and / or starch.

8. An enzyme granulated material according to claim 7, characterized in that it contains, as a water-insoluble filler, a mixture of cellulose, at least one zeolite or silicate, particularly layered silicate, and optionally at least one grain flour and / or legume flour.

9. A granulated enzyme material according to claim 1, characterized in that the water-insoluble filler is an alkali metal chloride, alkali metal acetate, alkali metal sulfate, calcium carbonate, lactose or a mixture thereof.

10. A granulated enzyme material according to claim 1, characterized in that the binder is a polyethylene glycol with a molecular weight of 200-1,000. a polyvinylpyrrolidone with molecular weights of 12,000-3,000,000, wheat starch and / or gluten;

11. A confounding enzyme granulated material with claim 1, characterized in that the humectant is a non-ionogenic surfactant preferably an alcohol ethoxylated with 5-85 ethoxy groups or a surfactant of the group of esters of sulfosuccinic acid

12. An enzyme granulated material according to claim 1, characterized in that the enzyme is a protease, amylase, hemylcellulose, lipase, oxireductase, lysozyme or any mixture thereof.

13. The use of the granulated enzyme material according to any of claims 1-12 in pulverized and / or granular detergent, cleanser, bleach or dishwashing formulations, particularly in dishwashing formulations containing bleach. The use according to claim 13, characterized in that the granulated enzyme material is used in detergent, cleansing, bleaching or dishwashing formulations, for objects made of silver or silver-coated objects.