Production of multi-enzyme granules

A process is presented for producing stable multi-enzyme containing granules. The process involves the steps of mixing a reversible competitive inhibitor with a first enzyme, adding a second incompatible enzyme, adding a carrier, extruding and granulating the resulting mixture and reducing the moisture content if necessary.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to enzyme granules containing at least two different 
enzymes, to a process for their production and to the use of the granules 
in solid or liquid detergents and cleaning formulations. 
2. Statement of Related Art 
Enzymes, especially proteases, are widely used in detergents, washing aids 
and cleaning products. Normally, the enzymes are not used as pure 
substances, but rather in the form of mixtures with a diluent/carrier 
material. If enzyme preparations of this type are added to conventional 
detergents, a considerable reduction in enzyme activity can occur during 
storage, especially if bleaching-active compounds are present. Application 
of the enzymes to carrier salts and simultaneous granulation in accordance 
with DE-OS 16 17 190 or by bonding using nonionic surfactants in 
accordance with DE-OS 16 17 188 or aqueous solutions of cellulose ethers 
in accordance with DE-OS 17 67 568 does not lead to a significant 
improvement in storage stability because the sensitive enzymes are 
generally situated on the surface of the carrier in mixtures of the type 
in question. Although the stability of the enzymes in storage can be 
significantly increased by coating the enzymes with or encapsulating them 
in the carrier material and converting them into the required particle 
form by extrusion, pressing and spheronizing, as described for example in 
DE-PS 16 17 232, in DE-OS 20 32 768 and in DE-ASS 21 37 042 and 21 37 043, 
corresponding enzyme preparations have poor solubility properties. The 
undissolved particles can become caught up in and thus soil the washing or 
pass into the wastewater without being used. Although the encapsulating 
compositions known from DE-OS 18 03 099, which consist of a mixture of 
solid acids or acidic salts and carbonates or bicarbonates and which 
disintegrate on addition of water, improve the solubility of the enzyme 
preparations, they are extremely sensitive to moisture and, accordingly, 
require additional protective measures. Another disadvantage of the 
above-mentioned preparation is that the enzymes can only be processed in 
the form of dry powders. The fermenter broths typically accumulating in 
the enzyme production process cannot be used in this form, but have to be 
freed from water beforehand. 
EP 168 526 describes enzyme granules which contain water-swellable starch, 
zeolite and a water-soluble granulation aid. This document proposes a 
production process for such formulations which overcomes the problem 
mentioned above and which essentially comprises concentrating a fermenter 
solution freed from insoluble constituents, introducing the additives 
mentioned and granulating the resulting mixture. The process using the 
additive mixture proposed therein is advantageously carried out with 
fermentation solutions which have been concentrated to a relatively high 
dry matter content, for example of 55% by weight. 
International patent application WO 92/11347 describes enzyme granules for 
use in granular detergents and cleaning compositions which contain 2% by 
weight to 20% by weight of enzyme, 10% by weight to 50% by weight of 
swellable starch, 5% by weight to 50% by weight of water-soluble organic 
polymer as granulation aid, 10% by weight to 35% by weight of cereal flour 
and 3% by weight to 12% by weight of water. These additives enable the 
enzyme to be processed without significant losses of activity. In 
addition, the storage stability of the enzymes in the granules is also 
satisfactory. 
As demonstrated by way of example by the documents cited above, a broad 
prior art exists in the field of the production of granular enzyme 
preparations, so that various possibilities for making up individual 
enzymes in particulate form are available to the expert. Unfortunately, 
the methods mentioned fail when two or more enzymes capable of reacting 
with one another are to be incorporated in the same granule. This problem 
arises in particular in connection with protease which, as a 
protein-degrading enzyme, is of course capable of decomposing a second 
enzyme and/or other enzyme present at the same time. If this decomposition 
process takes place during the production and/or storage of the enzyme 
granules, the effect of the second enzyme and/or other enzymes under 
in-use conditions is no longer guaranteed. 
Solutions to this problem have also been proposed in the prior art. Thus, 
according to International patent application WO 90/09440, two-enzyme 
granules are produced by coating a protease- and cellulose-containing core 
with a total of 10 layers (alternately stearic acid/palmitic acid 
glyceride and kaolin) the quantity of protective coating material in the 
Examples exceeding the quantity of core, subsequently applying a mixture 
of a second enzyme, a binder, a filler and a granulation aid and, finally, 
applying an outer coating. A production process such as this is 
unfavorable on account of the large amount of separating material required 
between the enzyme-containing core and the layer containing the second 
enzyme which lies further to the outside. Another disadvantage can be 
that, under in-use conditions, the enzyme on the outside dissolves first, 
the second enzyme only being released from the core at a later stage so 
that the two enzymes are unable to develop their effects at the same time. 
Hitherto unpublished German patent application DE 43 29 463 describes a 
process for the production of multi-enzyme granules in which two 
separately prepared batches of granules differing in size and each 
containing an enzyme are agglomerated in a subsequent co-granulation step. 
It is known from European patent application EP 304 332 that 
enzyme-containing basic granules can be coated with powder-form components 
containing a second enzyme. However, this method of producing multi-enzyme 
granules often leads to inadequate stability of the second enzyme present 
in the outer layer which, in addition, has to be prepared beforehand in 
powder form--another disadvantage of this method. In this variant, too, 
the two enzymes are generally not released simultaneously in the wash or 
cleaning liquor. 
DESCRIPTION OF THE INVENTION 
Accordingly, the problem addressed by the present invention was to provide 
a simple process for producing particulate enzyme preparations containing 
at least two different enzymes reacting with one another which would 
enable the enzymes to be incorporated in the multi-enzyme granules without 
any loss of activity and to remain therein in storage-stable manner. 
Surprisingly, this problem has been essentially solved by the use of a 
competitively reversibly inhibited enzyme in the form of an aqueous 
formulation which is mixed with more enzyme and additives and extruded in 
the form of this mixture. 
Accordingly, the present invention relates a process for the production of 
enzyme granules containing at least two different enzymes by mixing an 
aqueous liquid containing a first enzyme, which may optionally be a 
fermentation broth freed from insoluble constituents and concentrated, 
with a competitive inhibitor for this enzyme, subsequently mixing the 
primary enzyme with the second enzyme or with further enzymes, 
incorporating an organic and/or inorganic carrier material, extruding the 
resulting mixture of enzymes and additives through a multiple-bore die 
followed by a cutting unit, optionally spheronizing the extrudate in a 
spheronizing unit and drying and, if desired, applying an optionally dye- 
and/or pigment-containing coating. 
The present invention also relates to the use of the multi-enzyme granules 
obtainable in this way in detergents or cleaning compositions, more 
especially in particulate detergents or cleaning compositions. 
The process according to the invention provides enzyme granules which are 
suitable for incorporation in detergents and cleaning formulations and 
which are characterized in that they contain at least two different 
enzymes, more particularly enzymes which are capable of reacting with one 
another, i.e. which are not compatible with one another, in homogeneous 
distribution. The enzymes incompatible with one another may be 
incorporated together by the process according to the invention in 
granules in which they are present in substantially homogeneous form, but 
do not adversely affect one another. A crucial requirement in this regard 
is that the secondary enzyme should not be directly added to the 
concentrated aqueous primary enzyme solution, instead the primary enzyme 
should first be reversibly inactivated by a competitive inhibitor in the 
aqueous concentrate. Under in-use conditions, i.e. in water-containing 
wash or cleaning liquors, the inhibition of the primary enzyme is 
eliminated by the disintegration of the granule structure and by the 
dissolution of the inhibitor so that the primary and secondary enzymes 
develop their effects at more or less the same time. The primary enzyme is 
preferably protease while the secondary enzyme is preferably amylase, 
lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. 
The secondary enzyme may be incorporated in the primary enzyme in liquid 
form, for example as a commercial concentrate, or in solid made-up form, 
for example in the form of commercial granules. 
The primary enzyme present in the enzyme granules produced in accordance 
with the invention is, above all, protease obtained from microorganisms, 
such as bacteria or fungi. It may be obtained from suitable microorganisms 
by known fermentation processes which are described, for example, in 
DE-OSS 19 40 488, 20 44 161, 21 01 803 and 21 21 397, in U.S. Pat. Nos. 
3,632,957 and 4,264,738, in European patent application EP 006 638 and in 
International patent application WO 91/02792. Proteases are commercially 
available, for example, under the names BLAP.RTM., Savinase.RTM., 
Esperase.RTM., Maxatase.RTM., Optimase.RTM., Alcalase.RTM., Durazym.RTM. 
or Maxapem.RTM.. 
The primary enzyme is preferably present in the extrudates according to the 
invention in quantities of 1% by weight to 6% by weight. If the enzyme 
granules according to the invention are a protease-containing formulation, 
their protease activity preferably amounts to between 50,000 protease 
units (PU, as determined by the method described in Tenside 7 (1970), 125) 
and 350,000 PU and, more particularly, to between 100,000 PU and 250,000 
PU per gram of enzyme granules. 
The lipase suitable for use as the secondary enzyme or as a secondary 
enzyme component in the process according to the invention may be obtained 
from Humicola lanuginosa, as described for example in European patent 
applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, 
as described for example in International patent application WO 91/16422 
or in European patent application EP 384 717, from Pseudomonas species, as 
described for example in European patent applications EP 468 102, EP 385 
401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 
272 or EP 204 284 or in International patent application WO 90/10695, from 
Fusarium species as described, for example, in European patent application 
EP 130 064, from Rhizopus species as described, for example, in European 
patent application EP 117 553, or from Aspergillus species as described, 
for example, in European patent application EP 167 309. Suitable lipases 
are commercially obtainable, for example, under the names Lipolase.RTM., 
Lipozym.RTM., Lipomax.RTM., Amano.RTM. Lipase, Toyo Jozo.RTM. Lipase, 
Meito.RTM. Lipolase and Diosynth.RTM. Lipase. Lipase is preferably used in 
the process according to the invention in such quantities that the 
multi-enzyme granules contain 1 KLU/g (Kilo Lipase Units per gram 
according to the Novo standard method based on the enzymatic hydrolysis of 
tributyrin, as described in Novo Nordisk publication AF 95) to 80 KLU/g, 
preferably 1.5 KLU/g to 60 KLU/g and more preferably 2 KLU/g to 30 KLU/g. 
Multi-enzyme granules containing protease as the primary enzyme and amylase 
as the secondary enzyme are particularly suitable for use in dishwashing 
detergents, particularly machine dishwashing detergents. Suitable amylases 
are commercially available, for example, under the names Maxamyl.RTM. and 
Termamyl.RTM.. Amylase is preferably used in the process according to the 
invention in such quantities that the multi-enzyme granules contain 1 
KNU/g (Kilo Novo Units per gram according to the Novo standard method, 1 
KNU being the quantity of enzyme which degrades 5.26 g of starch at pH 
5.6/37.degree. C., based on the method described by P. Bernfeld in S. P. 
Colowick and N. D. Kaplan, Methods in Enzymology, Vol. 1, 1955, page 149) 
to 100 KNU/g, preferably 2 KNU/g to 60 KNU/g and more preferably 5 KNU/g 
to 50 KNU/g. 
The cellulase suitable for use as the secondary enzyme or as a secondary 
enzyme component may be an enzyme obtainable from bacteria or fungi which 
has an optimum pH preferably in the mildly acidic to mildly alkaline range 
of 6 to 9.5. Corresponding cellulases are known, for example, from DE-OSS 
31 17 250, 32 07 825, 32 07 847, 33 22 950 or from European patent 
applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 
550. They are preferably used in such quantities that the final 
multi-enzyme granules have a cellulolytic activity of 50 CEVU/g (Cellulose 
Viscosity Units per gram based on the enzymatic hydrolysis of 
carboxymethyl cellulose at pH 9.0/40.degree. C., as described in Novo 
Nordisk publication AF 253) to 1250 CEVU/g and, preferably, 100 CEVU/g to 
1000 CEVU/g. 
The production process according to the invention comprises mixing a first 
enzyme which is present in liquid form, for example in the form of an 
aqueous fermentation broth optionally freed from insoluble constituents, 
and which preferably has a water content below 35% by weight and, more 
particularly, from 5% by weight to 30% by weight with a competitive 
inhibitor for this enzyme. Such inhibitors include polyhydric alcohols, 
more particularly glycerol, propylene glycol, amino alcohols, for example 
mono-, di- and tri-ethanolamine and -propanolamine and mixtures thereof, 
lower carboxylic acids, for example as known from European patent 
applications EP 376 705 and EP 378 261, boric acid and alkali metal 
borates, boric acid/carboxylic acid combinations as known, for example, 
from European patent application EP 451 921, boric acid esters as known, 
for example, from International patent application WO 93/11215 or from 
European patent application EP 511 456, boric acid derivatives as known, 
for example, from European patent application EP 583 536, calcium salts, 
for example the calcium/formic acid combination known from European patent 
EP 28 865, magnesium salts as known, for example, from European patent 
application EP 378 262 and/or sulfur-containing reducing agents as known, 
for example, from European patent applications EP 080 748 or EP 080 223. 
The substances mentioned are preferably used in quantities of 20% by 
weight to 60% by weight and preferably in quantities of 35% by weight to 
50% by weight, based on the resulting mixture of water-containing enzyme 
and inhibitor. 
Suitable carrier materials for the enzyme mixture, which may be 
incorporated immediately afterwards, but more particularly only after 
addition of the secondary enzyme, are in principle any organic or 
inorganic powder-form substances which destroy or only reversibly 
deactivate the enzymes to a negligible extent, if at all, and which are 
stable under extrusion conditions. Corresponding substances are, for 
example, cellulose, maltodextrose, sucrose, invert sugar, glucose, 
starches, cereal flours, cellulose ethers, alkali metal alumosilicate, 
more particularly zeolite, layer silicate, for example bentonite or 
smectite, and water-soluble inorganic or organic salts, for example alkali 
metal chloride, alkali metal sulfate, alkali metal carbonate or alkali 
metal acetate, sodium or potassium being the preferred alkali metals. A 
mixture of starch, cereal flour, powder-form cellulose and sucrose and, 
optionally, cellulose ether and alkali metal carbonate is preferably used 
as the carrier material. If the secondary enzyme is used in solid form, it 
is generally present in the form of a powder or granules made up with such 
carrier materials. In one embodiment of the process according to the 
invention, there is no need in this case for the separate addition of 
carrier material. 
The starch suitable as the carrier material or as a component of the 
carrier material is preferably corn starch, rice starch, potato starch or 
mixtures thereof, corn starch being particularly preferred. Starch is 
preferably present in the carrier material for the enzyme mixture in 
quantities of 20 to 80% by weight and, more preferably, in quantities of 
25% by weight to 75% by weight, based on the carrier material as a whole. 
The sum total of the quantities of starch and flour is preferably not more 
than 95% by weight and, more particularly, is between 60% by weight and 
95% by weight. The cereal flour is in particular a product obtainable from 
wheat, barley, rye or oats or a mixture of these flours, whole-grain 
flours being preferred. A whole-grain flour in the context of the 
invention is understood to be a flour which has not been fully ground and 
which has been produced from whole non-dehulled grains or which consists 
at least predominantly of such a product, the rest consisting of fully 
ground flour or starch. Commercially available wheat flours, such as Type 
450 or Type 550, are preferably used. It is also possible to use ground 
products of the cereals leading to the starches mentioned above providing 
steps are taken to ensure that the flours have been produced from whole 
grains. It is known that the flour component of the additive mixture 
significantly reduces the odor of the enzyme preparation to an extent 
considerably greater than that achieved by incorporating corresponding 
starches in the same quantities. Corresponding cereal flour is preferably 
present in the carrier material for the primary enzyme in quantities of 
10% by weight to 35% by weight and, more preferably, in quantities of 15% 
by weight to 20% by weight. 
Granulation aids may be present as additional constituents of the carrier 
material, including for example cellulose or starch ethers, such as 
carboxymethyl cellulose, carboxymethyl starch, methyl cellulose, 
hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding 
cellulose mixed ethers, gelatine, casein, tragacanth or other 
water-soluble or readily water-dispersible oligomers or polymers of 
natural or synthetic origin. The synthetic water-soluble polymers include 
alkyl or alkenyl polyethoxylates, polyethylene glycols, polyacrylates, 
polymethacrylates, copolymers of acrylic acid with maleic acid or 
compounds containing vinyl groups, also polyvinyl alcohol, partly 
hydrolyzed polyvinyl acetate and polyvinyl pyrrolidone. Polyethylene 
glycols are preferably selected from those having average molecular 
weights of 200 to 3,000. If the granulation aids mentioned above are those 
containing carboxyl groups, they are normally present in the form of their 
alkali metal salts, more especially their sodium salts. Corresponding 
granulation aids may be present in the enzyme compounds suitable for the 
purposes of the invention in quantities of up to 10% by weight and, more 
particularly, in quantities of 0.5% by weight to 8% by weight, based on 
the multi-enzyme mixture to be extruded. The degree of substitution in 
carboxymethyl celluloses preferably used is in the range from 0.8 to 0.95 
because particularly strong granules are obtained where corresponding 
carboxymethyl celluloses are used or smaller quantities are required to 
obtain granules of a certain strength than where cellulose having a 
relatively low degree of substitution is used. In addition, by using the 
above-mentioned carboxymethyl cellulose with a relatively high degree of 
substitution, a higher throughput through the extruder can be achieved in 
the extrusion step of the granule production process. The degree of 
substitution of the carboxymethyl cellulose is understood to be the number 
of etherified oxygen atoms bearing a carboxymethyl group per saccharide 
monomer of the cellulose. 
The secondary enzyme present in solid or, preferably, liquid form may be 
added to the primary enzyme afterwards or before addition of the carrier 
material or granulation aid. The other constituents of the secondary 
enzyme optionally present in addition to the second enzyme are not 
critical although--for the preferred use of the enzyme granules according 
to the invention in detergents and cleaning compositions--typical 
ingredients of detergents and cleaning compositions or at least substances 
compatible therewith are preferably present. If the secondary enzyme is 
added in solid form, i.e. in admixture with carriers or diluents, this 
added component preferably contains inorganic salt, more particularly 
alkali metal sulfate and/or chloride, in quantities--based on the 
secondary enzyme preparation--of 30% by weight to 80% by weight, fibrous 
or powder-form cellulose in quantities of 2 to 40% by weight and binders, 
more particularly dextrose, sucrose, polyvinyl alcohol and/or polyvinyl 
pyrrolidone, in quantities of 0.1% by weight to 15% by weight. Made-up 
enzyme granules containing the secondary enzyme may also be used in the 
production process according to the invention. Accordingly, the particle 
containing the second enzyme may be produced by an extrusion process as 
described, for example, in International patent application WO 92/11347 or 
in European patent EP 168 526. Particulate secondary enzymes are 
preferably produced by pan granulation from an inorganic and/or organic 
carrier material and aqueous enzyme solution. A corresponding process 
using inorganic salt and cellulose fibers in the carrier material and 
water and/or a wax-like substance as binder is described, for example, in 
German patent DE 27 30 481. 
The enzyme granules according to the invention are preferably produced from 
aqueous primary enzyme fermenter broths which are freed from insoluble 
impurities, for example by microfiltration. The microfiltration is 
preferably carried out as crossflow microfiltration using porous tubes 
with micropores larger than 0.1 .mu.m in size, 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, as described, for example in European 
patent application EP 200 032. The microfiltration permeate is then 
concentrated, preferably by ultrafiltration optionally followed by vacuum 
evaporation. Concentration is preferably carried out in such a way that 
water contents of no more than 35% by weight are obtained. The concentrate 
is mixed with the secondary enzyme and a dry powder-form to granular 
mixture of the above-described carrier materials or extrusion aids 
preferably prepared in advance, addition in the reverse order or 
simultaneous addition also being possible. These additives are preferably 
selected from the carrier materials and extrusion aids mentioned in such a 
way that the multi-enzyme extrudate formed has an apparent density of 700 
g/l to 1200 g/l. The water content of the mixture to be extruded should be 
selected so that it can be converted during compounding with stirring and 
beating tools into granular particles non-tacky at room temperature and 
can be plastically deformed and extruded under relatively high pressures. 
The multi-enzyme mixture is then processed in basically known manner in a 
kneader and an adjoining extruder to form a plastic, substantially 
homogeneous paste which can undergo an increase in temperature to between 
40.degree. C. and 60.degree. C. and, more particularly, to between 
45.degree. C. and 55.degree. C. as a result of compounding. The material 
leaving the extruder is passed through a multiple bore die followed by a 
cutting blade so that it is reduced to cylindrical particles of 
predetermined size. The diameter of the bores in the multi-bore die is 
best from 0.7 mm to 1.2 mm and preferably from 0.8 mm to 1.0 mm. The 
length-to-thickness ratio of the extrudate is preferably in the range from 
0.9 to 1.1:1 and, more preferably, is 1.0:1. The particles present in this 
form may then be directly incorporated in detergents and cleaning 
compositions, optionally after a drying step. However, it has been found 
to be of advantage to spheronize the cylindrical particles leaving the 
extruder and cutter, i.e. to round them off and to "deflash" them in 
suitable machines. A corresponding spheronizing process is described, for 
example, in DE-OSS 21 37 042 and 21 37 043. It is carried out in a machine 
consisting of a cylindrical container with stationary, fixed side walls 
and a friction plate rotatably mounted on its base. Machines of this type 
are marketed under the name of Marumerizer.RTM.. After spheronizing, the 
still moist spherical particles are dried continuously or in batches, 
preferably in a fluidized bed dryer, at a temperature of preferably 
35.degree. C. to 50.degree. C. and, more particularly, at a maximum 
product temperature of 45.degree. C. to a residual moisture content of 4% 
by weight to 10% by weight and preferably 5% by weight to 8% by weight if 
they previously had higher water contents. At this stage of the process, 
any dust-like fractions smaller than 0.1 mm and, more particularly, 0.4 mm 
in size occurring during the production of the extrudate and any coarse 
fractions larger than 2 mm and, more particularly, 1.6 mm in size can be 
removed by sieving or air separation and optionally returned to the 
production process. The extrusion process is preferably carried out in 
such a way that the multi-enzyme extrudates formed have such a particle 
size distribution that less than 10% by weight and, more particularly, 
less than 2% by weight of the particles are smaller than 0.2 mm in 
diameter, 10% by weight to 20% by weight of the particles are 0.2 mm to 
less than 0.4 mm in diameter and 80% by weight to 90% by weight of the 
particles are from 0.4 mm to less than 0.8 mm in diameter. 
Substances for encapsulating and coating the extrudate particles may be 
additionally introduced after or preferably during the drying process. To 
this end, the drying step is preferably carried out by spraying the 
enzyme-containing particles in a fluidized bed with a typical binder 
which, in its most simple form, may be water. Other suitable binders are 
nonionic surfactants and, more particularly, film formers selected from 
the water-soluble organic polymers mentioned above, for example 
carboxymethyl cellulose and/or polyethylene glycol, which may be used as 
such or, more particularly, in the form of aqueous solutions. In addition, 
dyes or pigments may also be applied to the particles at the agglomeration 
stage in order to mask or modify any coloration present in the particles 
which generally emanates from the enzyme concentrate. Titanium dioxide and 
calcium carbonate have proved to be particularly suitable inert and 
physiologically safe pigments, being introduced subsequently or preferably 
together with the binder in the form of an aqueous dispersion. The water 
introduced with the pigment dispersion or with the binder is removed again 
during the drying step which is carried out at the same time or which may 
have to be carried out at a later stage. 
It is readily possible by the process according to the invention to obtain 
multi-enzyme granules which have the enzyme activity for each enzyme 
present theoretically expected from the activity of the individual enzymes 
used. In general, more than 90% and, in particular, more than 95% of the 
expected activity is maintained. 
The multi-enzyme granules obtainable in this way are preferably used for 
the production of solid, above all particulate detergents or cleaning 
products which may be obtained simply by mixing the multi-enzyme granules 
with other components typically used in detergents or cleaning products. 
Surprisingly, however, multi-enzyme granules according to the invention 
may also be incorporated in liquid or free-flowing and paste-like, 
water-free or water-containing formulations in which the multi-enzyme 
granules are insoluble, a distinct increase in the stability of the 
enzymes in storage by comparison with enzymes introduced in solution being 
obtained despite the simultaneous presence of incompatible enzymes. The 
viscosity of liquid formulations such as these is preferably in the range 
from 100 mPa.multidot.s to 60,000 mPa.multidot.s and may be adjusted 
within wide limits through the concentration in which soap and solvents, 
for example, are used. Protease/amylase granules according to the 
invention in particular are preferably used in machine dishwashing 
detergents which are preferably marketed as compacted powders with 
elevated apparent densities of, preferably, 750 to 1,000 g/l or in tablet 
form. Corresponding tablets are preferably produced by mixing the 
multi-enzyme granules with all the other ingredients in a mixer and 
tabletting the resulting mixture in conventional tablet presses, for 
example eccentric presses or rotary presses, under pressures of 
200.multidot.10.sup.5 Pa to 1500.multidot.10.sup.5 Pa. Breakage-resistant 
tablets which still dissolve sufficiently quickly under in-use conditions 
are readily obtained in this way, typically with flexural strengths in 
excess of 150 N. A correspondingly produced tablet preferably has a weight 
of 15 g to 40 g and, more particularly, 20 g to 30 g for a diameter of 35 
mm to 40 mm. 
For incorporation in particulate detergents and cleaning formulations, the 
enzyme granules preferably have average particle sizes of 0.9 mm to 1.8 mm 
and, more preferably, in the range from 1.0 mm to 1.5 mm. The granules 
produced in accordace with the invention preferably contain less than 5% 
by weight and, more preferably, at most 1% by weight of particles with 
sizes outside the 0.2 mm to 1.6 mm range. 
The enzyme preparation obtained in accordance with the invention consists 
of substantially rounded dust-free particles which generally have an 
apparent density of around 650 to 1050 grams per liter and, more 
particularly, 700 to 880 grams per liter. The granules produced in 
accordance with the invention are distinguished by very high stability in 
storage, particularly at temperatures above room temperature and at high 
atmospheric humidity levels, which--although enzymes capable of reacting 
with one another are present--generally exceeds even the stability in 
storage of individual enzymes made up separately from one another. This 
applies both to the enzyme granules according to the invention and to the 
enzyme granules according to the invention incorporated in particulate 
detergents or cleaning formulations. Another advantage of the enzyme 
granules according to the invention is their dissolving behavior under 
in-use conditions in the wash liquor in which all the enzymes present can 
be simultaneously released and can develop their cleaning effect. In a 
preferred embodiment, the granules according to the invention release at 
least 90% of their enzyme activity in water at 25.degree. C. within 3 
minutes and, more particularly, within 70 seconds to 2.5 minutes. 
Detergents or cleaning formulations containing multi-enzyme granules 
according to the invention or produced by the process according to the 
invention may contain other typical ingredients of such formulations which 
do not undesirably interact with the enzymes. The multi-enzyme granules 
are preferably incorporated in detergents or cleaning formulations in 
quantities of 0.1% by weight to 5% by weight and, more particularly, in 
quantities of 0.5% by weight to 2.5% by weight. 
It has surprisingly been found that enzyme granules having the properties 
described above synergistically influence the effect of certain other 
ingredients of detergents and cleaning compositions and that, conversely, 
the effect of the enzymes present in the multi-enzyme granules is 
synergistically enhanced by certain other detergent ingredients. These 
effects occur in particular in the case of nonionic surfactants, in the 
case of soil-releasing copolyesters, particularly those containing 
terephthalic acid units, in the case of water-insoluble inorganic 
builders, in the case of water-soluble inorganic and organic builders, 
more particularly based on oxidized carbohydrates, in the case of 
peroxygen-based bleaching agents, more particularly alkali metal 
percarbonate, and in the case of synthetic anionic surfactants of the 
sulfate and sulfonate type, but only to a negligible extent, if at all, in 
the case of alkyl benzene sulfonates, so that the ingredients mentioned 
are preferably used together with multi-enzyme granules according to the 
invention. 
In one preferred embodiment, a corresponding formulation contains nonionic 
surfactant selected from fatty alkyl polyglycosides, fatty alkyl 
polyalkoxylates, more particularly ethoxylates and/or propoxylates, fatty 
acid polyhydroxyamides and/or ethoxylation and/or propoxylation products 
of fatty alkyl amines, vicinal diols, fatty acid alkyl esters and/or fatty 
acid amides or mixtures thereof, more particularly in quantities of 2% by 
weight to 25% by weight. 
Another embodiment of such formulations is characterized by the presence of 
synthetic anionic surfactant of the sulfate and/or sulfonate type, more 
particularly fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty 
acid esters and/or sulfofatty acid disalts, more particularly in a 
quantity of 2% by weight to 25% by weight. The anionic surfactant is 
preferably selected from the alkyl or alkenyl sulfates and/or the alkyl or 
alkenyl ether sulfates in which the alkyl or alkenyl group contains 8 to 
22 carbon atoms and, more particularly, 12 to 18 carbon atoms. 
Suitable nonionic surfactants are the alkoxylates, more particularly the 
ethoxylates and/or propoxylates, of saturated or mono- to polyunsaturated 
linear or branched alcohols containing 10 to 22 and preferably 12 to 18 
carbon atoms. The degree of alkoxylation of the alcohols is generally 
between 1 and 20 and preferably between 3 and 10. They may be prepared in 
known manner by reaction of the corresponding alcohols with the 
corresponding alkylene oxides. Derivatives of the fatty alcohols are 
particularly suitable, although their branched-chain isomers, particularly 
so-called oxoalcohols, may also be used for the production of suitable 
alkoxylates. Accordingly, the alkoxylates, more particularly the 
ethoxylates, of primary alcohols containing linear groups, more 
particularly dodecyl, tetradecyl, hexadecyl or octadecyl groups and 
mixtures thereof are suitable. Corresponding alkoxylation products of 
alkyl amines, vicinal diols and carboxylic acid amides, which correspond 
to the alcohols mentioned in regard to the alkyl moiety, may also be used. 
Other suitable nonionic surfactants are the ethylene oxide and/or 
propylene oxide insertion products of fatty acid alkyl esters, which may 
be produced by the process described in International patent application 
WO 90/13533, and the fatty acid polyhydroxyamides which may be produced by 
the processes according to U.S. Pat. Nos. 1,985,424, 2,016,962 and U.S. 
Pat. No. 2,703,798 and International patent application WO 92/06984. 
So-called alkyl polyglycosides suitable for incorporation in the 
formulations according to the invention are compounds corresponding to the 
general formula (G).sub.n --OR.sup.1 where R.sup.1 is an alkyl or alkenyl 
group containing 8 to 22 carbon atoms, G is a glycose unit and n is a 
number of 1 to 10. Corresponding compounds and their production are 
described, for example, in European patent applications EP 92 355, EP 301 
298, EP 357 969 and EP 362 671 or U.S. Pat. No. 3,547,828. The glycoside 
component (G).sub.n is an oligomer or polymer of naturally occurring 
aldose or ketose monomers, including in particular glucose, mannose, 
fructose, galactose, talose, gulose, altrose, allose, idose, ribose, 
arabinose, xylose and lyxose. The oligomers consisting of such 
glycoside-bonded monomers are characterized not only by the type but also 
by the number of sugars present in them, the so-called degree of 
oligomerization. The degree of oligomerization n as an analytically 
determined quantity is generally a broken number, assuming a value of 1 to 
10 and, in the case of the glycosides preferably used, a value below 1.5 
and, more particularly, between 1.2 and 1.4. Glucose is the preferred 
monomer by virtue of its ready availability. The alkyl or alkenyl group 
R.sup.1 of the glycosides also preferably emanates from readily available 
derivatives of renewable raw materials, more particularly from fatty 
alcohols, although branched-chain isomers thereof, more particularly 
so-called oxoalcohols, may also be used for the production of suitable 
glycosides. Accordingly, primary alcohols containing linear octyl, decyl, 
dodecyl, tetradecyl, hexadecyl or octadecyl groups and mixtures thereof 
are particularly suitable. Particularly preferred alkyl glycosides contain 
a cocofatty alkyl group, i.e. mixtures with--essentially--R.sup.1 =dodecyl 
and R.sup.1 =tetradecyl. 
Nonionic surfactant is preferably present in formulations containing 
multi-enzyme granules according to the invention in quantities of 1 to 30% 
by weight and, more preferably, in quantities of 1% by weight to 25% by 
weight. 
The formulations in question may contain other surfactants instead of or in 
addition to those mentioned above, preferably synthetic anionic 
surfactants of the sulfate or sulfonate type, in quantities of preferably 
not more than 20% by weight and, more preferably, in quantities of 0.1% by 
weight to 18% by weight, based on the formulation as a whole. Alkyl and/or 
alkenyl sulfates containing 8 to 22 carbon atoms, in which an alkali 
metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion is 
present as countercation, are mentioned as particularly suitable synthetic 
anionic surfactants for use in such formulations. The derivatives of fatty 
alcohols containing in particular 12 to 18 carbon atoms and branched-chain 
analogs thereof, so-called oxoalcohols, are preferred. The alkyl and 
alkenyl sulfates may be produced in known manner by reaction of the 
corresponding alcohol component with a typical sulfating agent, more 
particularly sulfur trioxide or chlorosulfonic acid, and subsequent 
neutralization with alkali metal, ammonium or alkyl- or 
hydroxyalkyl-substituted ammonium bases. Corresponding alkyl and/or 
alkenyl sulfates are preferably present in the formulations containing 
multi-enzyme granules according to the invention in quantities of 0.1% by 
weight to 20% by weight and, more preferably, in quantities of 0.5% by 
weight to 18% by weight. 
Other suitable surfactants of the sulfate type are the sulfated 
alkoxylation products of the alcohols mentioned, so-called ether sulfates. 
These ether sulfates preferably contain 2 to 30 and, more preferably, 4 to 
10 ethylene glycol groups per molecule. Suitable anionic surfactants of 
the sulfonate type include the .alpha.-sulfoesters obtainable by reaction 
of fatty acid esters with sulfur trioxide and subsequent neutralization, 
more particularly the sulfonation products derived from fatty acids 
containing 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and 
linear alcohols containing 1 to 6 carbon atoms and preferably 1 to 4 
carbon atoms and the sulfofatty acids obtainable therefrom by formal 
saponification. 
Other optional surface-active ingredients are soaps, saturated fatty acid 
soaps, such as the salts of lauric acid, myristic acid, palmitic acid or 
stearic acid, and soaps derived from natural fatty acid mixtures, for 
example coconut oil, palm kernel oil or tallow fatty acids, being 
suitable. Soap mixtures of which 50% by weight to 100% by weight consist 
of saturated C.sub.12-18 fatty acid soaps and up to 50% by weight of oleic 
acid soap are particularly preferred. Soap is preferably present in 
quantities of 0.1% by weight to 5% by weight. However, larger quantities 
of soap, generally up to 20% by weight, may also be present, particularly 
in liquid formulations containing multi-enzyme granules according to the 
invention. 
In another embodiment, a formulation containing multi-enzyme granules 
according to the invention contains water-soluble and/or insoluble 
builders selected in particular from alkali metal alumosilicate, 
crystalline alkali metal silicate with a modulus of more than 1, monomeric 
polycarboxylate, polymeric polycarboxylate and mixtures thereof, more 
particularly in quantities of 2.5% by weight to 60% by weight. 
A formulation containing multi-enzyme granules according to the invention 
preferably contains 20% by weight to 55% by weight of water-soluble and/or 
water-insoluble organic and/or inorganic builders. The water-soluble 
organic builders include in particular those from the class of 
polycarboxylic acids, more particularly citric acid and sugar acids, and 
polymeric (poly)carboxylic acids, more particularly the polycarboxylates 
obtainable by oxidation of polysaccharides according to International 
patent application WO 93/16110, polymeric acrylic acids, methacrylic 
acids, maleic acids and copolymers thereof which may also contain small 
quantities of polymerizable substances with no carboxylic acid 
functionality in copolymerized form. The relative molecular weight of the 
homopolymers of unsaturated carboxylic acids is generally between 5,000 
and 200,000 while the relative molecular weight of the copolymers is 
between 2,000 and 200,000 and preferably between 50,000 and 120,000, based 
on free acid. A particularly preferred acrylic acid/maleic acid copolymer 
has a relative molecular weight of 50,000 to 100,000. Suitable, albeit 
less preferred, compounds of this class are copolymers of acrylic acid or 
methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl 
esters, ethylene, propylene and styrene, in which the percentage content 
of the acid is at least 50% by weight. Other suitable water-soluble 
organic builders are terpolymers containing two carboxylic acids and/or 
salts thereof as monomers and vinyl alcohol and/or a vinyl alcohol 
derivative or a carbohydrate as the third monomer. The first acidic 
monomer or its salt is derived from a monoethylenically unsaturated 
C.sub.3-8 carboxylic acid and preferably from a C.sub.3-4 monocarboxylic 
acid, more particularly from (meth)acrylic acid. The second acidic monomer 
or its salt may be a derivative of a C.sub.4-8 dicarboxylic acid, 
preferably a C.sub.4-8 dicarboxylic acid, maleic acid being particularly 
preferred. In this case, the third monomeric unit is derived from vinyl 
alcohol and/or preferably an esterified vinyl alcohol. Vinyl alcohol 
derivatives in the form of an ester of short-chain carboxylic acids, for 
example C.sub.1-4 carboxylic acids, with vinyl alcohol are particularly 
preferred. Preferred terpolymers contain 60% by weight to 95% by weight 
and, more particularly, 70% by weight to 90% by weight of (meth)acrylic 
acid or (meth)acrylate, preferably acrylic acid or acrylate, and maleic 
acid or maleate and 5% by weight to 40% by weight and preferably 10% by 
weight to 30% by weight of vinyl alcohol and/or vinyl acetate. Terpolymers 
in which the ratio by weight of (meth)acrylic acid or (meth)acrylate to 
maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 
3:1 and more preferably between 2:1 and 2.5:1 are most particularly 
preferred. Both the quantities and the ratios by weight mentioned are 
based on the acids. The second acidic monomer or its salt may also be a 
derivative of an allyl sulfonic acid substituted in the 2-position by an 
alkyl group, preferably a C.sub.1-4 alkyl group, or by an aromatic radical 
preferably derived from benzene or benzene derivatives. Preferred 
terpolymers contain 40% by weight to 60% by weight and, more particularly, 
45 to 55% by weight of (meth)acrylic acid or (meth)acrylate, preferably 
acrylic acid or acrylate, 10% by weight to 30% by weight and preferably 
15% by weight to 25% by weight of methallyl sulfonic acid or methallyl 
sulfonate and, as the third monomer, 15% by weight to 40% by weight and 
preferably 20% by weight to 40% by weight of a carbohydrate. This 
carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, 
mono-, di- or oligosaccharides being preferred and sucrose being 
particularly preferred. Predetermined weak spots are presumably 
incorporated in the polymer through the use of the third monomer, being 
responsible for the ready biodegradability of the polymer. These polymers 
may be prepared in particular by the processes described in German patent 
DE 42 21 381 and in German patent application P 43 00 772.4 and generally 
have a relative molecular weight in the range from 1,000 to 200,000, 
preferably in the range from 200 to 50,000 and more preferably in the 
range from 3,000 to 10,000. They may be used in the form of aqueous 
solutions, preferably in the form of 30 to 50% by weight aqueous 
solutions, especially for the production of liquid formulations. All the 
polycarboxylic acids mentioned are generally used in the form of their 
water-soluble salts, more particularly their alkali metal salts. 
The organic builders in question are preferably present in quantities of up 
to 40% by weight, more preferably in quantities of up to 25% by weight and 
most preferably in quantities of 1% by weight to 5% by weight. Quantities 
near the upper limit mentioned are preferably used in paste-form or liquid 
formulations, more particularly water-containing formulations, in which 
the multi-enzyme granules according to the invention are present. 
Suitable water-insoluble, water-dispersible inorganic builders are, in 
particular, crystalline or amorphous alkali metal alumosilicates which are 
used in quantities of up to 50% by weight, preferably in quantities of not 
more than 40% by weight and, in liquid formulations in particular, in 
quantities of 1% by weight to 5% by weight. Among these builders, 
detergent-quality crystalline alumosilicates, more especially zeolite NaA 
and optionally NaX, are particularly preferred. Quantities near the upper 
limit mentioned are preferably used in solid particulate formulations. 
Suitable alumosilicates in particular contain no particles larger than 30 
.mu.m in size, at least 80% by weight preferably consisting of particles 
less than 10 .mu.m in size. Their calcium binding capacity, which may be 
determined in accordance with German patent DE 24 12 837, is in the range 
from 100 to 200 mg CaO per gram. Suitable substitutes or partial 
substitutes for the alumosilicate mentioned are crystalline alkali metal 
silicates which may be present on their own or in the form of mixtures 
with amorphous silicates. The alkali metal silicates suitable as builders 
in the formulations preferably have a molar ratio of alkali metal oxide to 
SiO.sub.2 of less than 0.95 and, more particularly, in the range from 
1:1.1 to 1:12 and may be present in amorphous or crystalline form. 
Preferred alkali metal silicates are the sodium silicates, more 
particularly the amorphous sodium silicates, with a molar Na.sub.2 O to 
SiO.sub.2 ratio of 1:2 to 1:2.8. Amorphous alkali metal silicates such as 
these are commercially available, for example, under the name of 
Portil.RTM.. Those with a molar Na.sub.2 O:SiO.sub.2 ratio of 1:1.9 to 
1:2.8 may be produced by the process according to European patent 
application EP 0 425 427. They are preferably added as a solid and not in 
the form of a solution in the production process. Preferred crystalline 
silicates which may be present individually or in the form of a mixture 
with amorphous silicates are crystalline layer silicates with the general 
formula Na.sub.2 Si.sub.x O.sub.2x+1.yH.sub.2 O, in which x--the so-called 
modulus--is a number of 1.9 to 4 and y is a number of 0 to 20, preferred 
values for x being 2, 3 or 4. Crystalline layer silicates corresponding to 
this general formula are described, for example, in European patent 
application EP 0 164 514. Preferred crystalline layer silicates are those 
in which x in the general formula mentioned assumes a value of 2 or 3. 
.beta.- and .delta.-sodium disilicates (Na.sub.2 Si.sub.2 O.sub.5.yH.sub.2 
O) are particularly preferred, .beta.-sodium disilicate being obtainable 
for example by the process described in International patent application 
WO 91/08171. .delta.-Sodium silicates with a modulus of 1.9 to 3.2 may be 
prepared in accordance with Japanese patent applications JP 04/238 809 or 
JP 04/260 610. Substantially water-free crystalline alkali metal silicates 
corresponding to the above general formula, where x is a number of 1.9 to 
2.1, which have been prepared from amorphous alkali metal silicates as 
described in European patent applications EP 0 548 599, EP 0 502 325 and 
EP 0 452 428, may also be used in formulations containing multi-enzyme 
granules according to the invention. Another preferred embodiment of 
formulations according to the invention is characterized by the use of a 
crystalline sodium layer silicate with a modulus of 2 to 3 which may be 
produced from sand and soda by the process according to European patent 
application EP 0 436 835. Crystalline sodium silicates with a modulus of 
1.9 to 3.5 obtainable by the process according to European patents EP 0 
164 552 and/or EP 0 293 753 are used in another preferred embodiment of 
detergents or cleaning formulations containing multi-enzyme granules 
according to the invention. Their content of alkali metal silicates is 
preferably between 1% by weight and 50% by weight and more preferably 
between 5% by weight and 35% by weight, based on water-free active 
substance. If alkali metal alumosilicate, more particularly zeolite, is 
present as an additional builder, the alkali metal silicate content is 
preferably 1% by weight to 15% by weight and more preferably 2% by weight 
to 8% by weight, based on water-free active substance. In this case, the 
ratio by weight of alumosilicate to silicate, based on water-free active 
substances, is preferably 4:1 to 10:1. In formulations containing both 
amorphous and crystalline alkali metal silicates, the ratio by weight of 
amorphous alkali metal silicate to crystalline alkali metal silicate is 
preferably 1:2 to 2:1 and more preferably 1:1 to 2:1. 
In addition to the inorganic builder mentioned, other water-soluble or 
water-insoluble inorganic substances may be used in the formulations 
containing multi-enzyme granules according to the invention. Alkali metal 
carbonates, alkali metal hydrogen carbonates and alkali metal sulfates and 
mixtures thereof are suitable in this regard. This additional inorganic 
material may be present in quantities of up to 70% by weight, but is 
preferably absent altogether. 
The formulations may additionally contain other ingredients typical of 
detergents and cleaning formulations. These optional ingredients include 
in particular bleaching agents, bleach activators, heavy metal complexing 
agents, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic 
acids, polyphosphonic acids and/or aminopolyphosphonic acids, redeposition 
inhibitors, for example cellulose ethers, dye transfer inhibitors, for 
example polyvinyl pyrrolidone or polyvinyl pyridine-N-oxide, foam 
inhibitors, for example organopolysiloxanes or paraffins, solvents and 
optical brighteners, for example stilbene disulfonic acid derivatives. 
Formulations containing multi-enzyme granules according to the invention 
contain up to 1% by weight and, more particularly, from 0.01% by weight to 
0.5% by weight of optical brighteners, more particularly compounds from 
the class of substituted 
4,4'-bis-(2,4,6-triamino-s-triazinyl)-stilbene-2,2'-disulfonic acids, up 
to 5% by weight and, more particularly, from 0.1% by weight to 2% by 
weight of heavy metal complexing agents, more particularly aminoalkylene 
phosphonic acids and salts thereof, up to 3% by weight and, more 
particularly, 0.5% by weight to 2% by weight of redeposition inhibitors 
and up to 2% by weight and, more particularly, from 0.1% by weight to 1% 
by weight of foam inhibitors, the parts by weight mentioned being based on 
the formulation as a whole. 
Apart from water, solvents which are used in particular in liquid 
formulations containing multi-enzyme granules according to the invention 
and which may also be present in the liquid primary and/or secondary 
enzyme in the production process for the multi-enzyme granules according 
to the invention are preferably water-miscible solvents, including lower 
alcohols, for example ethanol, propanol, isopropanol and the isomeric 
butanols, glycerol, lower glycols, for example ethylene and propylene 
glycol, and the ethers derived from the classes of compounds mentioned. 
The multi-enzyme granules are present in undissolved form, i.e. in solid 
granular form, in these liquid formulations. 
The typical enzyme stabilizers optionally present, particularly in liquid 
formulations according to the invention, include amino alcohols, for 
example mono-, di-, tri-ethanolamine and -propanolamine and mixtures 
thereof, lower carboxylic acids as known, for example, from European 
patent applications EP 376 705 and EP 378 261, boric acid or alkali metal 
borates, boric acid/carboxylic acid combinations as known, for example, 
from European patent application EP 451 921, boric acid esters as known, 
for example, from International patent application WO 93/11215 or European 
patent application EP 511 456, boric acid derivatives as known, for 
example, from European patent application EP 583 536, calcium salts, for 
example the calcium/formic acid combination known from European patent EP 
28 865, magnesium salts as known, for example, from European patent 
application EP 378 262 and/or sulfur-containing reducing agents as known, 
for example, from European patent applications EP 080 748 or EP 080 223. 
Suitable foam inhibitors include long-chain soaps, more particularly 
behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, 
organopolysiloxanes and mixtures thereof which may additionally contain 
microfine, optionally silanized or otherwise hydrophobicized silica. For 
use in particulate formulations, these foam inhibitors are preferably 
fixed to granular water-soluble carriers as described, for example, in 
DE-OS 34 36 194, in European patent applications EP 262 588, EP 301 414, 
EP 309 931 or European patent EP 150 386. 
In addition, a formulation containing multi-enzyme granules according to 
the invention may contain redeposition inhibitors. The function of 
redeposition inhibitors is to keep the soil detached from the fibers 
suspended in the liquid and thus to prevent discoloration of the fibers. 
Redeposition inhibitors include water-soluble generally organic colloids, 
for example the water-soluble salts of polymeric carboxylic acids, glue, 
gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch 
or cellulose or salts of sulfuric acid esters of cellulose or starch. 
Water-soluble polyamides containing acidic groups are also suitable for 
this purpose. Soluble starch preparations and other starch products than 
those mentioned above, for example partly hydrolyzed starch, may also be 
used. Sodium carboxymethyl cellulose, methyl cellulose, methyl 
hydroxyethyl cellulose and mixtures thereof are preferably used. 
Another embodiment of a formulation containing multi-enzyme granules 
according to the invention contains bleaching agents based on peroxygen, 
more particularly in quantities of 5% by weight to 70% by weight, and 
optionally bleach activators, more particularly in quantities of 2% by 
weight to 10% by weight. The bleaching agents in question are the per 
compounds generally used in detergents, such as hydrogen peroxide, 
perborate which may be present as tetrahydrate or monohydrate, 
percarbonate, perpyrophosphate and persilicate which are generally present 
as alkali metal salts, more particularly sodium salts. These bleaching 
agents are preferably present in detergents containing multi-enzyme 
granules according to the invention in quantities of up to 25% by weight, 
more preferably in quantities of up to 15% by weight and most preferably 
in quantities of 5% by weight to 15% by weight, based on the detergent as 
a whole. The optional bleach activators include the N- or O-acyl compounds 
normally used, for example polyacylated alkylenediamines, more 
particularly tetraacetyl ethylenediamine, acylated glycol urils, more 
particularly tetraacetyl glycol uril, N-acylated hydantoins, hydrazides, 
triazoles, urazoles, diketopiperazines, sulfuryl amides and cyanurates, 
also carboxylic anhydrides, more particularly phthalic anhydride, 
carboxylic acid esters, more particularly sodium isononanoyl phenol 
sulfonate, and acylated sugar derivatives, more particularly pentaacetyl 
glucose. To avoid interaction with the per compounds in storage, the 
bleach activators may have been coated or granulated in known manner with 
shell-forming substances, tetraacetyl ethylenediamine with mean particle 
sizes of 0.01 mm to 0.8 mm granulated with carboxymethyl cellulose and 
obtainable, for example, by the process described in European patent EP 
037 026 and/or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine 
obtainable by the process described in German patent DD 255 884 being 
particularly preferred. These bleach activators are preferably present in 
detergents in quantities of up to 8% by weight and, more particularly, in 
quantities of 2% by weight to 6% by weight, based on the detergent as a 
whole. 
Finally, another embodiment of a formulation containing multi-enzyme 
granules according to the invention is characterized by the presence of 
soil release agents based on copolyesters of dicarboxylic acids and 
glycols which may be present in particular in quantities of 0.01 to 5% by 
weight. Soil release agents which are particularly effective by virtue of 
their chemical similarity to polyester fibers, but which are also capable 
of developing the required effect in fabrics of other materials are 
copolyesters containing dicarboxylic acid units, alkylene glycol units and 
polyalkylene glycol units. Soil-releasing copolyesters of the type 
mentioned and their use in detergents have been known for some time. For 
example, DE-OS 16 17 141 describes a washing process using polyethylene 
terephthalate/polyoxyethylene glycol copolymers. DE-OS 22 00 911 relates 
to detergents containing nonionic surfactant and a copolymer of 
polyoxyethylene glycol and polyethylene terephthalate. DE-OS 22 53 063 
describes acidic textile finishing formulations which contain a copolymer 
of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol 
and optionally an alkylene or cycloalkylene glycol. European patent EP 066 
944 relates to textile treatment formulations containing a copolyester of 
ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and 
sulfonated aromatic dicarboxylic acid in certain molar ratios. European 
patent EP 185 427 describes methyl- or ethyl-end-capped polyesters 
containing ethylene and/or propylene terephthalate and polyethylene oxide 
terephthalate units and detergents containing this soil-releasing polymer. 
European patent EP 241 984 relates to a polyester containing substituted 
ethylene units and glycerol units in addition to oxyethylene groups and 
terephthalic acid units. These soil-releasing polyesters are preferably 
present in formulations containing multi-enzyme granules according to the 
invention in quantities of 0.1% by weight to 2.5% by weight and more 
preferably in quantities of 0.2% by weight to 2% by weight. 
A corresponding detergent or cleaning formulation may also contain enzymes 
which have to be separately added, i.e. which are not incorporated through 
the multi-enzyme granules according to the invention. However, all enzymes 
present are preferably incorporated in the multi-enzyme granules. 
In one preferred embodiment, a formulation in which the multi-enzyme 
granules according to the invention or produced in accordance with the 
invention are incorporated is particulate and contains 20% by weight to 
55% by weight of inorganic builder, up to 15% by weight and, more 
particularly, 2% by weight to 12% by weight of water-soluble organic 
builder, 2.5% by weight to 20% by weight of synthetic anionic surfactant, 
1% by weight to 20% by weight of nonionic surfactant, up to 25% by weight 
and, more particularly, from 1% by weight to 15% by weight of bleaching 
agent, up to 8% by weight and, more particularly, from 0.5% by weight to 
6% by weight of bleach activator and up to 20% by weight and, more 
particularly, from 0.1% by weight to 15% by weight of inorganic salts, 
more particularly alkali metal carbonate and/or sulfate. 
In another preferred embodiment, a powder-form detergent intended in 
particular for use as a light-duty detergent contains 20% by weight to 55% 
by weight of inorganic builder, up to 15% by weight and, more 
particularly, from 2% by weight to 12% by weight of water-soluble organic 
builder, from 4% by weight to 24% by weight of nonionic surfactant, up to 
15% by weight and, more particularly, from 1% by weight to 10% by weight 
of synthetic anionic surfactant, up to 65% by weight and, more 
particularly, from 1% by weight to 30% by weight of inorganic salts, more 
particularly alkali metal carbonate and/or sulfate and neither bleaching 
agent nor bleach activator. 
Another preferred embodiment is a liquid formulation containing 5% by 
weight to 35% by weight of water-soluble organic builder, up to 15% by 
weight and, more particularly, from 0.1% by weight to 5% by weight of 
water-insoluble inorganic builder, up to 15% by weight and, more 
particularly, from 0.5% by weight to 10% by weight of synthetic anionic 
surfactant, from 1% by weight to 25% by weight of nonionic surfactant, up 
to 15% by weight and, more particularly, from 4% by weight to 12% by 
weight of soap and up to 30% by weight and, more particularly, from 1% by 
weight to 25% by weight of water and/or water-miscible solvent.

EXAMPLES 
Example 1 
A biomass-containing fermenter broth containing around 65,000 protease 
units per gram (PU/g) was obtained by fermentation of Bacillus 
licheniformis (ATCC 53926)--modified by the process described in 
International patent application WO 91/02792 by transformation of a gene 
sequence from Bacillus lentus DSM 5483--using the process described in 
German patent DE 29 25 427. The fermenter broth was concentrated to a 
protease content of 700,000 PU/g by decantation, crossflow 
microfiltration, ultrafiltration (cutoff limit at molecular weight 10,000) 
and subsequent concentration by evaporation in vacuo by the process 
described in International patent application WO 92/11347. 50 Parts by 
weight of propylene glycol were then added as inhibitor. The primary 
enzyme solution was then mixed with the commercially available liquid 
enzyme formulations listed in Table 1. 45 Parts by weight of cellulose 
powder (Technocel.RTM. 30, a product of Cellulose Fullstoff Fabrik), 35 
parts by weight of sucrose, 120 parts by weight of Na carboxymethyl 
cellulose (Tylose.RTM., a product of Hoechst AG), 50 parts by weight of 
polyethylene glycol (average molecular weight 2,000), 300 parts by weight 
of corn starch and 130 parts by weight of wheat flour were then added to 
the enzyme mixture in a mixer equipped with a rotating beating tool and 
the resulting mixture was homogenized in an externally cooled kneader. The 
plastic material was extruded in an extruder equipped with a multi-bore 
extrusion die (bore diameter 0.8 mm) and a rotating blade. The 0.8 mm long 
enzyme extrudates characterized by their enzyme composition in Table 1 
were obtained and were then powdered with 3 parts by weight of calcium 
carbonate and spheronized and deflashed for about 1 minute in a 
spheronizing machine (Marumerizer.RTM.) to form uniformly rounded 
particles. The material leaving the spheronizer was dried in a 
fluidized-bed dryer at temperatures of 40.degree. C. to 45.degree. C. and 
coated with 150 parts by weight of a coating material consisting of 
TiO.sub.2, stearyl alcohol and 40x ethoxylated castor oil. Particles 
smaller than 0.4 mm and larger than 1.6 mm in size (less than 1% by weight 
of all the particles) were subsequently removed by sieving. 
TABLE 1 
______________________________________ 
Enzyme Content of the Extrudates (Parts by Weight) 
E1 E2 E3 E4 
______________________________________ 
Protease broth 
190 190 300 190 
Amylase.sup.a) 
-- 20 
-- 
Lipase.sup.b) 
140 -- 
-- 
Cellulase.sup.c) 
-- 
-- -- 
140 
______________________________________ 
.sup.a) Termamyl .RTM. 300 L (liquid formulation; a product of Novo 
Nordisk) 
.sup.b) Lipolase .RTM. 100 L (liquid formulation; a product of Novo 
Nordisk) 
.sup.c) Celluzyme .RTM. 700 L (liquid formulation; a product of Novo 
Nordisk) 
Example 2 
The multi-enzyme granules E2 produced in Example 1 were mixed in a quantity 
of 1 part by weight with 99 parts by weight of a detergent with an 
apparent density of 780 g/l produced in accordance with WO 91/02047 
containing 18% by weight of sodium alkyl benzene sulfonate, 3% by weight 
of nonionic surfactant (Dehydol.RTM.), 16% by weight of sodium perborate, 
29% by weight of zeolite NaA, 5% by weight of sodium carbonate, 5% by 
weight of polymeric polycarboxylate (Sokalan CP 5, a product of BASF), 6% 
by weight of tetraacetyl ethylenediamine, 3% by weight of plasticizing aid 
(40x ethoxylated fatty alcohol) and--as the balance to 100% by 
weight--water (formulation W1). A mixture C1 which contained the same 
percentage of detergent and enzymes, but in which the two enzymes were 
distributed between two separate particles (protease granules according to 
International patent application WO 92/11347; Lipolase.RTM. 100 T, a 
product of Novodisk) was produced for comparison. The two formulations 
were stored for 6 weeks at 40.degree. C./80% relative air humidity. The 
enzyme activities (in arbitrary units) before and after storage are shown 
in Table 2 below. It can be seen that, in the detergent containing the 
multi-enzyme granules according to the invention, the stability of the 
enzymes present in one particle is significantly higher than when the 
enzymes are present in separate particles. The same surprising finding 
also applies to the multi-enzyme extrudates E1, E3 and E4 of Example 1. 
TABLE 2 
______________________________________ 
Enzyme Activities 
Protease Activity 
Lipase Activity 
______________________________________ 
W1: Start 142 38 
after 6 weeks' storage 
136 34 
C1: Start 75117 
after 6 weeks' storage 
75 52 
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