EP0694060A1

EP0694060A1 - Enzymatic washing agent

Info

Publication number: EP0694060A1
Application number: EP94913117A
Authority: EP
Inventors: Heidi Andexer; Horst Upadek
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-04-13
Filing date: 1994-04-05
Publication date: 1996-01-31
Anticipated expiration: 2014-04-05
Also published as: WO1994024258A1; ATE161284T1; DE59404831D1; ES2110744T3; EP0694060B1; JPH08508775A; DE4312010A1

Abstract

The aim of the invention is to provide a washing agent which is based on enzymes alone and avoids, as far as possible, other usual washing-agent components, and which has a washing power at least equal to that of ordinary washing agents with an optimized composition. The enzymatic washing agent according to the invention contains protease, lipase, amylase and cellulase plus, optionally, small quantities of surfactants and/or builders. Washing agents with this kind of composition can be used as stand-alone washing agents or as washing auxiliaries in addition to ordinary washing agents.

Description

"Envv atic detergent"

The invention relates to an enzyme-based detergent which contains protease, lipase, amylase and cellulase and optionally surfactant and / or builder.

Detergents and auxiliary washing agents which contain enzymes have been known for a long time. In particular, proteolytic enzymes have been used in textile detergents for over 60 years and have proven to be a very effective cleaning component against protein stains. In this connection, by way of example only, reference is made to the German patent application DT 16 17 189, from which detergents containing protease and bleaching agents are known. Detergents which, in addition to protease, additionally contain amylase as an active ingredient for removing soils based on starch are known, for example, from German Offenlegungsschrift DE 27 27 463. In connection with detergents which contain lipase as a fat-removing active ingredient, reference is made, for example, to European patent applications EP 478050, relating to a preferably liquid detergent with lipase and a stabilizer which reversibly complexes with the catalytically active site of the enzyme, EP 468 102 ¬ appropriate detergents with anionic and / or nonionic surfactant and lipase from Pseudomonas plantarii and optionally Builder, EP 381 431, relating to aqueous liquid detergents with certain lipase, 0.1-10% polyalkylene glycol ester and 5-35% surfactant and optionally protease, EP 376 705, regarding liquid detergents with 10-90% surfactant, which consists of at least 50% nonionic surfactant, 1-10% C] __ 4-alcohol, 0.1-5% Cι_3 ~ carboxylic acid, lipase and protease, EP 373850, regarding a Detergent which contains 1-60% by weight of surfactants containing a primary alkyl sulfate and a lipase in certain quantities in addition to the usual ingredients t, EP 368589, relating to granular detergents with lipase, 6-35% by weight of soap-free anionic and / or nonionic surfactant and at least 456% by weight of builder, which consists of at least 28% by weight of Na zeolite, citrate, carbonate and / or layered silicate.

In contrast, the advantageous effect of cellulolytic enzymes is not primarily in the field of removing textile stains, but rather is based on the textile softening, color-refreshing and textile surface image-improving properties of this enzyme. Cellulase-containing detergents are, for example, from European patent applications EP 120528, relating to a textile-softening detergent which contains 2 to 50% by weight of anionic surfactant and / or nonionic surfactant, 0.5 to 15% by weight of a tertiary A ins and contains a cellulase, EP 177 165, relating to a fabric softening detergent which contains a clay mineral and cellulase, EP 173398, relating to a detergent containing cellulase and a mono- or di-long-chain, primary or secondary amine, EP 173397, concerning an alkaline detergent which contains 2 to 50% by weight of anionic surfactant and / or nonionic surfactant, 0.5 to 15% by weight of cationic fabric softener, up to 80% by weight of builder and a cellulose from fungi, and EP 269 169, relating to a detergent containing cellulase and a diamine or polyamine with tertiary nitrogen or a corresponding ammonium compound, is known. Detergents which contain a combination of up to three enzymes are also known, for example the combination of 0.1 to 2% by weight of protease, 0.2 to 1% by weight of cellulase and up to 2% by weight .-% amylase from European patent application EP 365 103 and the combination of protease, amylase and lipase or cellulase from European patent application EP 425214.

All these known agents have the disadvantage that they have, in addition to the enzyme components, a large number of other ingredients which, in terms of their amounts and their composition, require careful optimization in order to obtain the desired cleaning result. The applicant had set itself the goal of developing a detergent which, as far as possible solely on the basis of enzymes, with the greatest possible avoidance of other conventional detergent components, has a washing performance which at least achieves that of conventional detergents which are highly optimized in their composition. This object was achieved by providing a detergent with a combination of at least four different types of enzyme.

The invention accordingly relates to an enzymatic detergent which contains protease, lipase, amylase and cellulase and optionally surfactant and / or builder.

Another object of the invention is the use of an enzymatic washing aid which has a proteolytic activity of preferably 10,000 PU / g to 75,000 PU / g, a lipolytic activity of preferably 10,000 LU / g to 90000 LU / g, has an amylolytic activity of preferably 1 KNU / g to 20 KNU / g and a cellulolytic activity of preferably 5 IU / g to 150 IU / g, as a cleaning-enhancing additive to detergents or bleaches or aqueous liquors, the detergents or contain bleach.

The protease which can be used according to the invention is an enzyme which can be obtained from microorganisms, in particular bacteria or fungi, with a pH optimum in the alkaline range. Suitable proteases are known, for example, from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416967 or EP 394352. Protease is preferably used in the agent according to the invention in amounts such that the finished agent is 10,000 PU / g to 75,000 PU / g (protease units per gram, determined according to the method described in Tideside 7, 125 (1970)), in particular 12500 PE / g to 65000 PE / g and particularly preferably 15000 PE / g to 45000 PE / g. Useful proteases are commercially available, for example under the names Savinase ( ^R ), Esperase ( ^R ), Maxatase ( ^R ), 0ptimase ( ^R ) or Alcalase ( ^R ).

The lipase contained in the agent according to the invention is also an enzyme that can be obtained from microorganisms, in particular bacteria or fungi. Such are known for example from the European patent applications EP 204208, EP 214761, EP 258068, EP 407225 or the international patent application WO 87/859. Useful commercially available lipases are, for example, Lipolase ( ^R ) and Lipozym'R). Lipase is used in Agents according to the invention are preferably used in amounts such that the finished agent 10,000 LU / g to 90000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 according to that in EP 258068 mentioned method), in particular 15,000 LU / g to 80,000 LU / g and particularly preferably 20,000 LU / g to 55,000 LU / g.

The amylase which can be used according to the invention is an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the alkaline range, up to about pH 10. Useful commercial products are, for example, Termamyl ( ^R ) and Maxamyl ( ^R ). Amylase is preferably used in the agent according to the invention in amounts such that the finished agent 1 KNU / g to 20 KNU / g ("Klo-Novo-Um ^' ts" per gram according to the Novo standard method, 1 KNU the Is the amount of enzyme that breaks down 5.26 g of starch at pH 5.6 and 37 ° C., based on the method described by P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, page 149), in particular 1.5 KNU / g to 18 KNU / g and particularly preferably 3 KNU / g to 16 KNU / g.

Likewise, the cellulase which can be used according to the invention is an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the almost neutral to weakly alkaline pH range from 6 to 9.5. Such cellulases are known, for example, from German patent applications DE 31 17 250, DE 3207825, DE 3207847, DE 3322950 or European patent applications EP 265832, EP 269977, EP 270974, EP 273 125 and EP 339 550. They are preferably used in the agent according to the invention in amounts such that the finished agent has a cellulolytic activity of 5 IU / g to 150 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethyl cellulose) pH 9.0 and 40 ° C, as described in Agric. Biol. Chem. 53, 1275 (1989) by S. Ito et al.), in particular 7.5 IU / g to 140 IU / g and particularly preferred 12 IU / g to 130 IU / g. Suitable commercial products are, for example, Celluzyme ( ^R ) from Novo Industri or KAC ( ^R ) from Kao.

The agents according to the invention can be in the form of liquid, paste-like or solid preparations, in particular in the case of liquid or paste-like detergents the presence of conventional enzyme stabilizers, such as, for example, boron compounds, for example organoboronic acids or boric acid or alkali borates, alkali metal carboxylates, for example sodium formate, glycols, for example glycerol, ethylene glycol or propylene glycol, amino alcohols, for example mono-, di- or triethanol - or -propanolamine, or alkaline earth metal ions, for example calcium ions, may be desirable.

In a preferred embodiment, the detergents according to the invention are in particle form. In detergents of this type, the enzymes mentioned are embedded in the form adsorbed on carrier substances, in coating substances or in the form of customary granules with inorganic and / or organic carrier materials, as described, for example, in German patent DE 16 17 232, the German Published documents DT 20 32766 or DE 4041 752 or the European patent applications EP 168526, EP 170360, EP 270608 or EP 304331 are used. The enzymes can be contained separately in up to four separate particles or in the form of multi-enzyme granules, as described, for example, in the international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein.

In addition to the enzymatic active ingredients, the detergents according to the invention can contain all known ingredients that are usually present in detergents. In addition to the optionally stabilized enzymes, however, only surfactant and / or builder is preferably present, these also being able to be used in significantly smaller amounts than is customary in conventional detergents. As a rule, the presence of very small amounts of surfactant is sufficient to achieve washing performance that is not inferior to that of known universal detergents with significantly higher surfactant contents. The detergents according to the invention therefore preferably contain no more than 10% by weight, in particular from 0.5% by weight to 5% by weight, based on the total agent, of surfactant. Builders and surfactants are preferably entirely absent from the washing aids according to the invention. The contingent components mentioned below and their amounts are to be understood exclusively as the amounts of such ingredients which may be present in the enzyme particles. The surfactant optionally contained in the agents according to the invention is anionic, nonionic, cationic or amphoteric surfactant or mixtures thereof, preferably nonionic surfactant of the alkyl polyalkoxylate type, optionally in a mixture with synthetic anionic surfactant of sulfate - Or sulfonate type is used. The nonionic surfactants in question include alkyl glycosides and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding saturated or unsaturated alcohols with the corresponding alkylene oxides. Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers can also be used to prepare usable alkoxylates. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexcdecyl or octadecyl radicals and mixtures thereof are particularly useful. Also the alkoxylation products, especially the ethoxylation products, of mono- or polyunsaturated fatty alcohols, for example oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and Eruca. heard ge, can be used. Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl moiety can also be used. The ethoxylation and / or Propcxylierungs- products of fatty acid Ci-bis-CTJ alkyl esters, Ahren as ^f by the method described in International Patent Application WO 90/13533 Ver her¬ can be provided, and / or fatty acid polyhydroxyamides, they wia can be produced in accordance with international patent application WO 92/6984, can be used. The agents according to the invention have particularly good cleaning properties if the nonionic surfactant component is an alkoxylated, in particular ethoxylated, fatty alcohol with an average degree of alkoxylation of 5 to 10, preferably 6 to 8.

Suitable sulfonate surfactants are, in particular, alkylbenzenesulfonates with linear Cg to Ci5 alkyl groups on the benzene nucleus, which are present as alkali metal or ammonium salts. Suitable anionic surfactants of the sulfonate type The α-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization also belong, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms -Atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as the sulfofatty acid disalts derivable from these.

The useful surfactants of the sulfate type include, in particular, primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. The derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octa-decyl radicals. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating agent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.

In addition, the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates, can be present in the compositions. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.

The agents according to the invention can contain up to 40% by weight, preferably not more than 20% by weight and in particular 1% by weight to 5% by weight, of builder. Suitable water-soluble organic builder substances are, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain small amounts of polymerizable substances without a carboxylic acid functionality in copolymerized form. The acids mentioned are usually in the form of their alkali salts, in particular special of their sodium or potassium salts used. Organic builder substances of this type are preferably present in amounts of up to 30% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing, detergents according to the invention.

In particular, crystalline or amorphous alkali alumosilicates, in amounts of not more than 40% by weight, preferably not more than 20% by weight and in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the crystalline aluminosilicates, in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, granular detergents. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist at least 80% by weight of particles below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12837, is in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the alumosilicate mentioned are crystalline, layered alkali silicates, as are described, for example, in European patent application EP 164 514 and can be obtained by the process of international patent application WO 91/8171.

In addition to the inorganic builder mentioned, further water-soluble or water-insoluble inorganic substances can be used in the agents according to the invention. In this context, the alkali silicates, alkali carbonates, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable. Such additional inorganic material can be present in amounts up to 10% by weight, but is preferably absent entirely.

The agents according to the invention can be used to set a weakly alkaline pH, if desired, in particular from about 8.0 to 9.5 in 1% by weight aqueous solution, solid inorganic and / or organic acids or acidic salts, for example alkali metal bisulfates, succinic acid, Adipic acid or glutaric acid and mixtures thereof. The- Like acidic substances are contained in the agents according to the invention preferably in amounts of not more than 5% by weight, in particular from 0.1% by weight to 3% by weight.

In addition, the agents according to the invention can contain further constituents customary in detergents, in particular complexing agents for heavy metals, for example amino polycarboxylic acids and / or polyphosphonic acids or their salts, graying inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinylpyrrolidone, foam inhibitors, for example organopolysiloxanes or Paraffins, and another enzyme, especially oxidase, peroxidase and / or collagenase, belong. Such ingredients can be contained in the agents according to the invention in amounts of up to 5% by weight, in particular from 0.1% by weight to 4% by weight.

The agents according to the invention can be produced in the simplest manner by mixing the enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, with optional other powdery constituents and, if desired, also liquid or liquefied constituents which in particular include nonionic surfactants, but also colorants and fragrances, can be mixed in by spraying. If the detergent according to the invention is to contain other components in addition to the enzymatic active ingredients, it is preferred to convert these components, insofar as they are thermally resilient, into a powder product in a known manner by spray drying an aqueous slurry and to convert this with the enzymes active ingredients and optionally other thermally sensitive constituents, to which bleaching agents in particular, for example alkali perborates or alkali percarbonate, are to be counted. The incorporation of the other constituents by admixing a granulate or extrudate containing them with the enzymatic constituents is also possible and is particularly preferred for the production of detergents according to the invention with a relatively high bulk density of preferably 650 g / 1 to 900 g / 1. The detergents according to the invention are gentle on the dye and fabric, have excellent cleaning performance, possess, probably in particular due to their lipase content, graying-inhibiting action and, probably in particular due to their cellulase content, give soft laundry. It is noteworthy that these positive effects already occur at doses which are significantly below the dosage of about 6 g / 1 to 8 g / 1 wash liquor customary for typical European household universal detergents.

Examples

example 1

The compositions M1 to M4 characterized in Table 1 below by their composition were prepared by simply mixing the enzyme granules in the quantities indicated.

Table 1; Composition of funds TGew .--% 1

Ml M2 M3 M4

Protease ³ ) 25 30 30 -

Protease ⁰ ) - - - 25

Lipase ⁰ ) 25 54 50 25

Amylase ^) 25 10 12 25

Cellulase ^e ) 25 6 8 -

Cellulase ^f ) - - - 25

a) BLAP ( ^R ) granules (manufacturer Biozym), activity 147000 PE / gb) BLAP ( ^R ) granules (manufacturer Biozym), activity 170000 PE / gc) Lipolase ( ^R ) granules (manufacturer Novo), activity 100000 LU / gd) Termamyl ( ^R ) granules (manufacturer Novo), activity 60 KNU / ge) KAC ( ^R ) granules (manufacturer Kao), activity 500 IU / gf) Celluzyme ( ^R ) granules (manufacturer Novo), activity 700 IU / g

Cotton textile pieces provided with standardized stains were washed in a launderometer with the washing liquors listed in Table 2 (WL: 0.32 g / 1 sodium lauryl sulfate, 0.16 g / 1 7-fold ethoxylated Ci2-18 ~ alcohol, 1, 2 g / 1 zeolite Na-A; W2: Wl and 1.6 g / 1 enzyme mixture Ml; W3: 0.64 g / 1 sodium lauryl sulfate, 0.32 g / 1 7-fold ethoxylated Ci2-l8 ^_alcohol , 1 , 2 g / 1 zeolite Na-A; W4: W3 and 1.6 g / 1 enzyme mixture Ml) washed (test conditions: 2 g soiled fabric and 6 g non-soiled filler fabric, 100 ml washing liquor, water hardness 16 ° d, temperature 40 ° C, washing duration including heating-up time 30 minutes; Evaluation by remission measurement at 460 n, without UV). The results shown in Table 2 were found. For comparison, a washing liquor H5 with a commercially available liquid detergent containing 13.5% by weight nonionic surfactant (12% by weight 7-fold ethoxylated fatty alcohol and 1.5% by weight Ci2 / i4 ~) was used under the same conditions Alkyl glucoside), 5% by weight anionic surfactant (Na-Ciδ / iß-alkyl sulfate), 14% by weight soap, 7% by weight 1,2-propylene glycol, 5% by weight ethanol, balance to 100% by weight Water, tested in the prescribed dosage of 7.5 g / 1.

Table 2: Remission of the washed test fabrics T% 1

Washing remission in the case of Schmt fleet S / H ³ ) BMT °) BMR °) ^{, tzu} ! ) MK ^e )

Wl 45.9 32.3 61.5 43.7 29.2

W2 52.1 47.3 67.9 74.2 43.3

W3 49.8 32.4 63.6 51.3 32.3

W4 58.9 49.0 67.9 75.4 45.6

W5 51.1 39.4 64.7 57.9 37.7

a) dust / skin fat b) blood / milk / ink c) blood / milk / soot d) milk / soot e) milk / cocoa

It can be seen that the addition of the er.zymatisehen agent according to the invention in small doses to the fleets W1 and W3 containing only low concentrations of builder and surfactant, which, as expected, only show inadequate washing performance, achieves washing performance which corresponds to that of a outperform conventional liquid detergents, even if this is used in a significantly higher dosage. It is also noteworthy that in some cases a Viaschflotte, which contained only Ml (dosage 1.6 g / 1), a Wc-.schleistung had that which at least corresponds to that of the higher-dose liquid detergent (fleet W5 in Table 2)).

Example 2

In order to demonstrate the advantageous effect of an enzymatic detergent according to the invention, even under practical conditions, a liquid detergent containing 25% by weight of 7-fold ethoxylated C 1-5 fatty alcohol, 2% by weight of C] .2 / l4- Alkyl glucoside, 5% by weight Na-Ci2 / 14-alkyl sulfate, 16% by weight soap, 5% by weight glycerin, 7% by weight ethanol, the remainder to 100% by weight water, perfume and salts . In a commercially available household washing machine (Miele W701), the artificial soiling specified in the table below, fixed on barley grain towels, was washed together with 3.5 kg of clean household laundry at 40 ° C. (colored washing program normal, amount of water 20 l, Düsseldorf city water). The evaluation of the primary washing result was carried out as indicated in Example 1 by means of the remission (average of 3 determinations). The dosage was 1.5 g / 1 of the liquid detergent and 1.6 g / 1 of the agent M4 from Example 1.

Table 3: Remission of test fabrics T% 1 washed under practical conditions

Soiling Remission after washing Initial value (fluctuation range)

Dust on cotton 73.3 (1.9) 36.2

Dust / skin fat on cotton 73.0 (0.4) 26.8

Dust / skin oil on polyester 74.7 (0.5) 31.4

Red wine on cotton 47.5 (0.5) 31.6

Milk / carbon black on cotton 74.0 (1.0) 18.0

The washing performance using the washing aid according to the invention was in all cases significantly better than that of the liquid detergent alone, even if 0.1% by weight of amylase (Termamyl ( ^R ) LDX 300) and 2% by weight of water were added to it. -% protease (alkali se () 2.5 LDX) and then used the resulting enzymatic liquid detergent in a significantly higher dosage (4.6 g / 1).

Claims

1. Enzyme-containing detergent, characterized in that it contains protease, lipase, amylase and cellulase and not more than 10% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and / or not more than 40% by weight of builder contains.

2. Composition according to claim 1, characterized in that it contains protease in the amount that it has a proteolytic activity of 10000 PE / g to 75000 PE / g.

3. Composition according to claim 1 or 2, characterized in that it contains lipase in the amount that it has a lipolytic activity of 10000 LU / g to 90000 LU / g.

4. Composition according to one of claims 1 to 3, characterized in that it contains amylase in the amount that it has an a ylolytic activity of 1 KNU / g to 20 KNU / g.

5. Composition according to one of claims 1 to 4, characterized in that it contains cellulase in the amount that it has a cellulolytic activity of 5 IU / g to 150 IU / g.

6. Composition according to one of claims 1 to 5, characterized in that it contains 0.5 wt .-% to 5 wt .-% surfactant, in particular nonionic surfactant.

7. Composition according to one of claims 1 to 6, characterized in that it does not contain more than 20% by weight, in particular 1% by weight to 5% by weight, of water-soluble or water-dispersible builder substances, in particular zeolite Na-A, contains.

8. Composition according to claim 7, characterized in that it contains, as surfactant, an ethoxylation product of a primary linear alcohol having 10 to 22 carbon atoms, in particular 12 to 18 carbon atoms, the average degree of ethoxylation of which is 5 to 10, in particular 6 to 8.

9. Composition according to one of claims 1 to 8, characterized in that it is in particle form and the enzymes are used in granular form, adsorbed on carrier materials.

10. Use of an enzymatic washing aid which has a proteolytic activity of in particular 10,000 PE / g to 75,000 PU / g, a lipolytic activity of in particular 10,000 LU / g to 90,000 LU / g, an amylolytic activity of in particular 1 KNU / g to 20 KNU / g and a cellulolytic activity of in particular 5 IU / g to 150 IU / g, as a cleaning-enhancing additive to detergents or bleaches or aqueous liquors which contain detergents or bleaches.