DE4041752A1 - ENZYME PREPARATION FOR WASHING AND CLEANING AGENTS - Google Patents

Abstract

In the production of enzyme granulates with grain sizes from 0.1 to 2 mm, containing 2 to 20 % wt. proteases, lipases, amylases and/or cellulases, 10 to 50 % wt. swellable starch, 5 to 50 % wt. granulating agent, 3 to 12 % wt. water and not more than 10 % wt. water-soluble salt, by extruding an enzyme pre-mixture obtained by mixing a fermentation liquor cleared of insoluble components and concentrated with additives and spheroidizing the extrudate in a rounder, the use of relatively highly concentrated fermentation liquours has previously been necessary. By removing the insoluble components from the fermentation liquor by micro-filtration and mixing with additives which, in relation to the finished granulate, contains 10 to 35 % wt. cereal flour, it is possible, by the use of low-concentration fermentation liquors, to obtain highly active enzyme granulates with a long shelf life which are suitable for inclusion in washing and cleansing agents and are distinguished by uniform solubility properties in aqueous washing and cleansing baths.

Description

The invention relates to an enzyme granules, a method for his Her position and use of the granules in solid washing and cleaning convey.

Enzymes, in particular proteases, find extensive use in washing, Detergents and cleaners. Usually, the enzymes come here not as concentrates, but in mixtures with a dilution and Carrier material used. If one mixes such enzyme preparations usual Detergents, so when storing a significant degradation of Enzymak tivity, especially when bleach-active compounds are present are. The application of the enzymes to carrier salts with simultaneous Gra tion according to the German patent application DT 16 17 190 or by sticking with nonionic surfactants according to the German Of Designation DT 16 17 118 or aqueous solutions of cellulose ethers according to the German Offenlegungschrift DT 17 87 568 does not lead to a significant improvement in storage stability, since the sensitive Enzymes in such mixtures usually on the surface of the Trä gersubstanz are located. Although the storage stability of the enzymes can be essential can be increased if the enzymes are coated with the carrier material be entrapped in this and then by extrusion, Presses and Marumerisieren converted into the desired particle shape, such as For example, in German Patent DE 16 17 232, the German Publication DT 20 32 768, and the German Auslegeschriften DE 21 37 042 and DE 21 37 043 described. Have such enzyme preparations but only poor solubility properties. The undissolved particles can get caught in the laundry and contaminate it or they will unused transferred to the sewage. From the German patent application DT 18 03 099 known embedding, consisting of a mixture of solid  Acids or acidic salts and carbonates or bicar consist of bonates and disintegrate when water is added, although they improve the dissolving power, But they are very sensitive to moisture and therefore require additional protective measures.

Another disadvantage of the above preparation is the fact that the enzymes can only be processed in the form of dry powders. The usually leave fermentation broths produced in the enzyme production do not commit themselves in this form, but have previously dehydrated who the. To this condition, such procedures are bound, in which only slightly soluble carrier materials, such as sugar, starch and Cellulose ethers as a binder for the preparation of enzyme preparations be set.

From European patent EP 1 68 526 enzyme granules are known, the water-swellable starch, zeolite and water-soluble granules tools included. This document describes a manufacturing process proposed for such formulations, which essentially be in it is to aufzubring a freed from insoluble components fermenter solution concentrate with the above aggregates and that granulate resulting mixture. The procedure with which there presented Suggested aggregate mixture is advantageous with fermentation solutions carried out on a relatively high dry matter content, at For example, 55 wt .-%, have been concentrated. In addition, the thus produced granules a high solution or Zer fall speed under washing conditions, so that the enzymes under Circumstances are deactivated relatively quickly.

It was therefore the object, by a manufacturing process that the Use of low-concentrated fermentation broths allowed the pulping properties, in particular the uniform solubility of the known Pro improve the activity losses in enzyme processing to further reduce and the shelf life of the enzymes even further increase. This object is achieved by the invention described below solved.  

The invention relates to a for incorporation in washing and cleaning suitable enzyme granules with a particle size of 0.1 mm to 2 mm, containing from 2% to 20% by weight of protease, amylase and / or cellulase, calculated as dry substance, from 10% by weight to 50% by weight of swellable starch, 5 wt .-% to 50 wt .-% granulation, which is a water-soluble or contains ganic polymer, not more than 10 wt .-% of water-soluble salt and 3 wt .-% to 12 wt .-% water, which is characterized in that it Contains 10 wt .-% to 35 wt .-% cereal flour, and its use for Production of granular detergents and cleaners.

Furthermore, the invention relates to a process for the preparation of one of like enzyme granules by extruding one by mixing one of insoluble components liberated and concentrated fermentation broth with aggregates formed enzyme premix, spheronization the extrudate in a Rondiergerät, drying and optionally on bringing a dye or pigment-containing coating of water-soluble Lich, film-forming polymer, wherein the method characterized is that the insoluble constituents from the fermentation broth through Microfiltration removed and the concentrated fermentation broth with an aggregate containing from 10% to 35% by weight of cereal flour, based on finished granules containing.

As enzymes come primarily from microorganisms, such as bacteria or fungi, recovered proteases, lipases, amylases and / or cellulases in question, wherein proteases produced by Bacillus species and their mixtures with amylases are preferred. They are fermented in a known manner obtained from suitable microorganisms, for example in German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, the US patents US 36 32 957 and US 42 64 738 and the European patent application EP 0 06 638 are described. Particularly advantageous can the erfindungsge appropriate method for the formulation of the very active proteases of the so-called second generation, for example Savinase® and related enzymes whose storage-stable incorporation in washing and detergent usually causes problems. According to the invention it is possible, the resulting in the fermentation processes broths  Extracellular enzymes after separating the insoluble impurities by Microfiltration and subsequent concentration by ultrafiltration and optionally subsequent evaporation in vacuo immediately in storable, largely odorless granules to transfer. The Ent tion of unwanted enzyme dusts and the additional drying pro Zessen occurring activity losses are avoided.

Enzymes are in the granules according to the invention preferably in amounts of 4 wt .-% to 20 wt .-% included. If it is in the inventive Enzyme granules is a protease-containing formulation is the Protease activity preferably 70,000 protease units (PE, determined according to the method described in Tenside 7 (1970), 125) to 250,000 PE, esp especially 140,000 PE to 200,000 PE, per gram of enzyme granules.

The water-swellable starch is preferably Corn starch, rice starch, potato starch or mixtures thereof, wherein the use of corn starch is particularly preferred. Swellable strength is in the enzyme granules of the invention in amounts of 10 wt .-% to 50 wt .-%, in particular from 20 wt .-% to 40 wt .-%, wherein the Preferably, do not sum the amounts of swellable starch and flour over 60 wt .-%, in particular 32 wt .-% to 55 wt .-% is.

In the corn flour suitable according to the invention is in particular This is a product made from wheat, rye, barley or oats or a mixture of these flours, Whole Wheat Flours being preferred. Un ter a wholemeal flour is in the context of the invention, a not fully out grinded flour made from whole, unpeeled grains has been or at least predominantly from such a product be stands, the remainder of fully ground flour or starch consists. Preferably, commercially available wheat flour qualities, such as Type 450 or Type 550, used. Also the use of flour products the leading to above-mentioned swellable starches cereals is possible if care is taken to make the flours out of the whole grains have been produced. Due to the flour component of the aggregate amount Mix is a significant odor reduction of the enzyme preparation achieved, which the odor reduction by the incorporation of the same  Far surpasses quantities of corresponding starches. Such Ge is in the enzyme granules of the invention in amounts of 10 wt .-% to 35 wt .-%, in particular from 12 wt .-% to 25 wt .-% ent hold.

Furthermore, the enzyme granules of the invention contain 5 wt .-% to 50 wt .-%, preferably 15 wt .-% to 25 wt .-% granulation, the contains at least one water-soluble organic polymer. Suitable Ver For example, compounds of this class are cellulose and starch ethers, such as Carboxymethyl cellulose, carboxymethyl starch, methyl cellulose, hydroxy ethylcellulose, hydroxypropylcellulose and corresponding cellulose mixture ether. Optionally, gelatin, casein, tragacanth, Maltodextro sucrose, invert sugar, glucose syrup or others soluble in water or readily dispersible oligomers or polymers natural ur jump are used. Useful synthetic water-soluble polymers are polyethylene glycol, polyacrylates, polymethacrylates, copolymers of Acrylic acid with maleic acid or vinyl group-containing compounds, further Polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinylpyrrolidone. As far as the aforementioned compounds are those with free Carboxyl groups, they are usually in the form of their sodium salts.

In addition, the enzyme granules can be water-insoluble granulation aids to which in particular cellulose and phyllosilicates, at For example, bentonites or smectites belong.

Combinations of 8% by weight to 20% by weight have proven to be particularly suitable. Sodium carboxymethyl cellulose and 3 wt .-% to 10 wt .-% polyethylene glycol the latter having a molecular weight of preferably from 1000 to 20,000, in particular from 2000 to 15,000. The sodium carboxy methylcellulose sets the disintegration and dispersion rate of Gra nulate in cold washings. By adding polyethylene Glycol may have this effect towards a higher dissolution rate be changed. At the same time, this addition makes it easier Spheronizing the granules. As an additional Granulierhilfsmittel the granules according to the invention a combination of preferably 2 wt .-%  to 10% by weight of cellulose and preferably 2% by weight to 3% by weight of sucrose or a combination of preferably from 2% to 10% by weight of cellulose and preferably from 2% to 5% by weight of a compound selected from Group comprising sorbitol, maltodextrin, polyvinylpyrrolidone, amylogum and containing their mixtures.

As further ingredients, the granules can still small amounts, before preferably not more than 10% by weight, in particular from 1% by weight to 10% by weight contain water-soluble salts which are selected so that they La not adversely affect the stability of the enzymes. These salts can the disintegration and dispersion of the granules in particular especially in cold washings. Suitable salts are, for example Sodium chloride, sodium sulfate, sodium acetate, potassium acetate or their Mixtures.

For the preparation of the enzyme granules according to the invention, one starts from Fer made by microfiltration of insoluble impurities be freed. The microfiltration is preferably as a cross Stream microfiltration using porous pipes with micropores larger 0.1 μm, flow rates of the concentrate solution of more than 2 m / s and a pressure difference to the permeate side of less than 5 bar performed as For example, in European Patent Application EP 2 00 032 described. Subsequently, the microfiltration permeate is preferably by Ultra filtration, optionally followed by vacuum evaporation aufkon centered. A particular advantage of the invention is the fact that the concentration can be conducted so that one only relatively low dry matter contents of preferably 5% by weight to 50% by weight, in particular from 10 wt .-% to 40 wt .-% passes. The concentrate becomes egg in a suitably prepared before dry, powdery bis granular mixture of the above-described additives metered. The Water content of the mixture should be chosen so that they are in the Machining with stirring and impact tools in granular, at room temperature transfer non-sticky particles and, if higher pressures are used, pla deformed and extruded.  

The free-flowing premix is then known in principle known in a kneader and a connected extruder to a plastic Processed mass, whereby as a result of mechanical processing, the Mass to temperatures between 40 ° C and 60 ° C, in particular 45 ° C to 55 ° C. can warm up. The material leaving the extruder is passed through a perforated disc be guided with subsequent cutting blade and thereby zylinderförmi crushed particles of defined size. Appropriately, the Diameter of the holes in the perforated disc 0.4 mm to 1 mm, preferably 0.5 mm to 0.9 mm. The particles present in this form can Closing dried and fed to later use. It has However, proved to be advantageous, the ver the extruder and chopper subsequently spheronizing, that is to say, the leaving cylindrical particles round off and deburr them in suitable devices. Such Sphäronisierungsverfahren is for example in the German Aus Legnotes DE 21 37 042 and DE 21 37 043 described. One uses For this purpose, a device consisting of a cylindrical container with statio nary, solid side walls and a bottom rotatably mounted friction plate exist. Devices of this type are under the trade name Marumerizer® spread in the art.

After spheronization, the still wet beads become continuous or batchwise, preferably using a Wirbelschichttroc kenanlage, preferably at most 45 ° C, in particular a maximum of 40 ° C per product temperature up to a residual moisture content of 3 wt .-% to 12 wt .-%, preferably 6 wt .-% to 8 wt .-% dried. After or preferably During drying, additional materials for wrapping and Beschich th of the particles are introduced. Suitable coatings are in particular the film formers under the aforementioned water-soluble organic Polymers, preferably higher molecular weight, that is a molecular weight from 1000 to 20 000 having polyethylene glycols. You can continue at this stage also dyes or pigments on the particles bring to a possible own color, mostly from the enzyme concentrate is due to cover or change. As inert and phy Siologically harmless pigment has in particular be titanium dioxide which is preferably introduced in aqueous dispersion. The above the pigment dispersion or via the polymer solution supplied  Water is taken at the same time or subsequently again required drying again removed.

Through sieving or wind sifting may occur dusty Shares with a particle size less than 0.1 mm, preferably less than 0.2 mm and possible coarse fractions with a grain size over 2 mm, preferably over 1.6 mm away and possibly back into the manufacturing process be guided. The granules of the invention preferably contain we less than 5% by weight, in particular not more than 1% by weight, of particles with grain sizes outside the range of 0.2 mm to 1.6 mm.

The enzyme preparation obtained consists of largely rounded, dust free particles, which usually have a bulk density of about 500 to 900 grams per liter, in particular 650 to 880 grams per liter. It is preferably used for the production of solid, especially granular Detergents or cleaning agents used. Your enzyme activity may be at Use of protease-containing fermenter broths, due to the flexible Dry matter content of the broths before mixing with the additive to values in the range of preferably 70,000 to 250,000 proteases units per gram (PE / g), in particular from 140,000 to 200,000 PE / g be presented. The granules of the invention are characterized by their low odor and, even in a mixture with detergents and cleaners as well as per compounds, by a very high storage stability, in particular at temperatures above room temperature and high humidity, as well as a uniform solution behavior in the wash liquor. As a further advance It should be appreciated that the enzyme granules according to the invention are present in water 25 ° C within 2 minutes, preferably not more than 90% and inner preferably over 97% of its enzymatic activity within 5 minutes and thus a sufficiently long exposure time of the enzyme to enzymatic removable stains, especially in aqueous washing or cleaning lye, ensure.

Examples example 1

By fermentation of Bacillus licheniformis analogous to the process described in German Patent DE 29 25 427 3.3 m ^{3 of} a biomass-containing fermenter broth was obtained, which contained about 50 000 protease units per gram (PE / g). The pH of the fermenter broth was adjusted by addition of 33gewichtsprozentiger CaCl solution to about 7.5. At closing coarse impurities were removed by decantation. The broth was diluted with water to a volume of 11.5 m ³ . The separation of the enzyme from the cell mass was carried out by means of cross-flow microfiltration (membrane pore diameter 0.14 μm). This gave about 24 m ³ microfiltration permeate with about 7000 PE / g. By ultrafiltration (separation limit at molecular weight 10,000) of the enzyme-containing filtrate and subsequent evaporation in vacuo (50 mbar, temperature up to 30 ° C) was obtained 0.3 m ^{3 of} a broth F1 having a dry matter content of 35 wt .-% and a protease content of 500 000 PE / g. The broths F2 (28% by weight dry substance, 480,000 PE / g), F3 (19% by weight dry substance, 350,000 PE / g) and F4 (38% by weight dry matter, by similar procedure were prepared from similar fermenter broths. 600 000 PE / g). The thus concentrated Fermen terbrühen F1 to F4 were mixed in a equipped with rotating impact tool mixer with the additives listed in Table 1 and homogenized in a provided with an external cooling kneader. The extrusion of the plastic mass was carried out by means of a disk with a hole (hole diameter 0.7 mm) and a rotating knife equipped th extruder. The extrudates E1 to E5 characterized by their composition were obtained in Table 1 by lengths of 0.7 mm to 1 mm in a spheronizing apparatus (Marumerizer®) during a processing time of about 5 minutes with simultaneous dusting with powdered calcium carbonate (3 Wt .-%) were deformed and deburred to rounded particles. The material leaving the spheronizer was dried in a fluidized-bed dryer at temperatures of 40 ° C. to 45 ° C. within about 15 minutes to a water content of about 6% by weight. By subsequent sieving, particles with particle sizes below 0.2 mm and above 1.6 mm were largely removed, which were recycled to the process at the stage of mixing with the additives. The enzyme granules were coated by spraying an aqueous titanium dioxide pigment suspension and then spraying an aqueous polyethylene glycol solution during the fluidized-bed drying. The end products G1 to G5 having the enzyme activities indicated in Table 2 were thus obtained from the extrudates E1 to E5.

Table 1

Composition of the extrudates [% by weight]

Table 2

Enzyme activity of the granules [PE / g]

Example 2

To determine the dissolution rate, as described in EP 1 68 526 1 gram of enzyme granules in 100 ml of water stirred by magnetic stirrer of 16 ° dH (160 mg CaO / l) at 25 ° C. After every 1 minute were Taken samples and their enzyme activity after filtering off undissolved Be constituents determined. The ranges given in Table 3 were found from 3 determinations, the dissolution rates of the according to Example 1 ago granules G1 to G5 did not differ significantly.

Rate of enzyme release Time released activity [Minutes] [%] 1 60-70 2 83-86 3 93-97 5 100

Example 3

2 grams of the enzyme granules G2 were mixed with 98 grams of a commercial Vollwaschmittels (Perboratgehalt 18 Gew. -%) mixed and in a Kar clay container made of unbacked cardboard at 30 ° C and 80% relative air stored moisture. For comparison, a sample was the same  Amount of commercial granules of an alkaline protease (Savina se® 4.0 T, manufacturer Novo Industri A / S), under the same Conditions stored. The samples showed storage periods of 2 and 4 Weeks the enzyme activities indicated in Table 4 (based on set activity = 100%). The activity of further erfindungsge The enzyme granules according to Example 1 differed after storage not significantly different from granulate G2. The washing performance of the 62hal Detergent to proteinaceous soils was the one of the comparative detergent in no case inferior.

Table 4

Storage stability in a detergent formulation (30 ° C, 80% relative humidity)

Claims (14)

1. Enzyme granules suitable for incorporation in detergents or cleaners having a particle size of 0.1 mm to 2 mm, containing 2% by weight to 20% by weight of protease, lipase, amylase and / or cellulase, calculated as dry substance , 10 wt .-% to 50 wt .-% swellable starch, 5 wt .-% to 50 wt .-% granulation aid containing a water-soluble organic polymer, not more than 10 wt .-% of water-soluble salt and 3 wt. -% to 12 wt .-% water, characterized in that it contains 10 wt .-% to 35 wt .-% cereal flour. 2. Enzyme granules according to claim 1, characterized in that it is 4 wt .-% to 20% by weight of protease, lipase, amylase and / or cellulase, in particular protease, 20 wt .-% to 40 wt .-% swellable starch, esp Rice starch, 15 wt .-% to 40 wt .-% Granulierhilfsmittel and Contains 12 wt .-% to 25 wt .-% cereal flour, the sum of the Amounts of swellable starch and flour not exceeding 60% by weight, in particular 32 wt .-% to 55 wt .-% is. 3. Enzyme granules according to claim 1 or 2, characterized in that the Flour from the group comprising wheat flour, rye flour, barley flour, Oatmeal and their mixtures is selected. 4. Enzyme granules according to any one of claims 1 to 3, characterized gekennzeich net that it is protease with an activity of 70 000 PE to 250 000 PE, in particular 140 000 PE to 200 000 PE, per gram of enzyme granules ent holds. 5. Enzyme granules according to any one of claims 1 to 4, characterized gekennzeich net, that it as granulation 8 wt .-% to 20 wt .-% carboxy Methylcellulose and 3 wt .-% to 10 wt .-% polyethylene glycol with a average molecular weight of 1000 to 20,000. 6. Enzyme granules according to claim 5, characterized in that it as to additional granulation a combination of 2 wt .-% to 10 wt .-% cellulose and 2 wt .-% to 3 wt .-% sucrose or a  Combination of 2 wt .-% to 10 wt .-% cellulose and 2 wt .-% bis 5% by weight of a compound selected from the group comprising sorbitol, Maltodextrin, polyvinylpyrrolidone, amylogum and mixtures thereof ent holds. 7. Enzyme granules according to claim 5 or 6, characterized in that it as additional granulating agent not exceeding 10% by weight of phyllosilicate contains and the sum of the amounts of phyllosilicate and carboxy methyl cellulose does not exceed 20% by weight. 8. Enzyme granules according to any one of claims 1 to 7, characterized gekennzeich net, that it is 1 wt .-% to 3 wt .-% of a water-soluble salt, the an alkali chloride, an alkali metal sulfate, an alkali metal acetate or a mixture out of these is. 9. Enzyme granules according to one of claims 1 to 8, characterized gekennzeich net, that it is covered with a dye or pigment-containing coating water-soluble, film-forming polymer is coated. 10. Enzyme granules according to any one of claims 1 to 9, characterized gekennzeich net, that it is less than 5 wt .-%, preferably at most 1 wt .-% of Particles with grain sizes outside the range of 0.2 mm to 1.6 mm having. 11. Enzyme granules according to one of claims 1 to 10, characterized gekennzeich net, that in water at 25 ° C within 2 minutes not more than 90% and within 5 minutes more than 97% of its enzyme activity releases. 12. A process for producing an enzyme granulate having a particle size from 0.1 mm to 2 mm, the 2% by weight to 20% by weight protease, lipase, Amylase and / or cellulase, calculated as dry substance, 10% by weight to 50% by weight of swellable starch, 5% by weight to 50% by weight of granules agent containing a water-soluble organic polymer, 3 wt .-% to 12 wt .-% water and not more than 10 wt .-% water-soluble Salt by extruding one by mixing one of un  Soluble components and concentrated fermentation broth with additives produced enzyme premix, Sphäroni tion of the extrudate in a Rondiergerät, drying and given if applying a dye or pigment containing coating made of water-soluble, film-forming polymer, characterized that the insoluble components from the fermentation broth through Microfiltration removed and the concentrated fermentation broth mixed with an aggregate, the 10 wt .-% to 35 wt .-% cereal demehl, based on finished granules contains. 13. The method according to claim 12, characterized in that the flour the group comprising wheat flour, rye flour, barley flour, oatmeal and their mixtures are selected. 14. Use of an enzyme granulate according to any one of claims 1 to 11 for Production of solid, especially granular detergents and cleaners.