EP2313483B1 - Method for improving the cleaning action of a detergent or cleaning agent - Google Patents

Description

The present application is directed to the use of a polyanionic substance to improve the cleaning performance of a detergent containing a protease.

The use of enzymes in detergents and cleaners is well established in the art. They serve to extend the range of services of the funds concerned according to their specific activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three hydrolyze proteins, starches and fats and thus contribute directly to soil removal. Cellulases are used in particular because of their tissue effect. Another group of washing and cleaning agent enzymes are oxidative enzymes, in particular oxidases, which, if appropriate, in combination with other components, are preferably used to bleach soiling or to produce the bleaching agents in situ. In addition to these enzymes, which are subjected to constant optimization, further enzymes are constantly being made available for use in detergents and cleaners in order to be able to optimally address particular soiling, such as pectinases, β-glucanases, mannanases or other hemicellulases for hydrolysis, in particular more specific vegetable polymers.

The enzymes that have long been established and are contained in virtually all modern, high-performance detergents and cleaners are proteases, and in particular serine proteases, which include the subtilases. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are attributed to the serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. An overview of this family, for example, the article " Subtilases: Subtilisin-like Proteases "by R. Siezen, pages 75-95 in" Subtilisin enzymes ", edited by R. Bott and C. Betzel, New York, 1996 , Subtilases are naturally produced by microorganisms; Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Examples of the subtilisin-type proteases preferably used in detergents and cleaners are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, Subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases, but no longer to the subtilisins in the narrower sense. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime and Properase ® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P From Amano Pharmaceuticals Ltd., Nagoya, Japan, and that available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Favorably, there are synergy effects between the enzymes and the other constituents of the respective detergents or cleaners.

A disadvantage of these enzymes used in detergents and cleaning agents, in particular proteases, from the prior art is that they are especially at low temperatures, for example between 10 ° C and 40 ° C, in particular between 10 ° C and 30 ° C or even between 10 ° C and 25 ° C, have no satisfactory hydrolytic activity, in particular proteolytic activity, and therefore in particular in detergents and dishwashing detergents in this temperature range show no optimal cleaning performance.

Surprisingly, it has been found that the addition of certain substances considerably improves the cleaning performance of detergents and cleaners containing hydrolytic enzymes, in particular proteases, in particular at comparatively low temperatures, in particular between 10 ° C. and 50 ° C., between 10 ° C. and 40 ° C and preferably between 10 ° C and 30 ° C and 10 ° C and 25 ° C.

US 6,235,697 B1 describes protease-containing detergents which additionally contain surfactants, cellulase and an acrylic acid-based homo- or copolymer. EP 2 083 067 A1 describes the use of organic complexing agents and / or polymeric carboxylic acid group-containing compounds in a liquid detergent or cleaning composition to improve the washing or cleaning performance at a temperature of 40 ° C.

The present invention is therefore based on the object to improve the cleaning performance (washing power) of detergents or cleaning agents, in particular with regard to soiling, which are sensitive to degradation by proteases in a temperature range between 10 ° C and 30 ° C and 10 ° C. and 25 ° C. Another object of the invention is the cleaning performance of hydrolytic enzymes, in particular proteases, in detergents or cleaning or the to improve by the washing or cleaning agent formed wash liquor, in particular with regard to soiling, which are sensitive to degradation by proteases in a temperature range between 10 ° C and 30 ° C and 10 ° C and 25 ° C.

The invention thus relates to the use of a polyanionic substance for achieving a synergistic enzyme-based cleaning performance in interaction with a protease in a washing or cleaning agent when using the washing or cleaning agent, characterized in that it is carried out in a temperature range of 10 to 30 ° C. becomes. Preferred embodiments are given in claims 2-7.

According to the invention, it has been found that the cleaning performance of detergents or cleaners, in particular with regard to their enzymatic, in particular proteolytic, cleaning performance, is significantly improved if these agents comprise at least one protease (also referred to herein as component (a)) with one or more polyanionic substances ( Also referred to herein as component (b)) is combined. In the context of the invention, cleaning performance is understood to mean the whitening performance of one or more soiling, in particular laundry soiling, which are sensitive to degradation by proteases. Examples of such stains are blood milk / ink on cotton, full egg / pigment on cotton, chocolate milk / ink on cotton, peanut oil pigment / ink on polyester / cotton, grass on cotton or cocoa on cotton, especially such as indicated below. In the context of the invention, both the washing or cleaning agent, which comprises the hydrolytic enzyme or the washing or cleaning liquor formed by this agent, and the hydrolytic enzyme itself have a respective cleaning performance. The cleaning performance of the hydrolytic enzyme thus contributes to the cleaning performance of the agent or the washing or cleaning liquor formed by the agent.

The cleaning performance of detergents and cleaning agents based on the enzymatic activity used, in particular on the proteolytic activity, is improved by the addition of component (b). With regard to the interaction of these components (a) and (b), a synergistic effect results, ie a better performance compared to the individual performances of the respective component in one-component systems (ie detergents or cleaners, each containing only the hydrolytic, in particular proteolytic enzyme, or contain component (b)) and also with respect to the sum of the individual performances of components (a) and (b), ie the sum of two one-component systems each having the component (a) and (b ) alone. Thus, the selected combination of hydrolytic enzyme (a), ie protease, with a component (b) according to the invention provides a further possibility in order to improve the performance of detergents with regard to their cleaning performance, in particular their enzyme-based cleaning performance, especially with regard to their cleaning performance, which is brought about by a protease contained.

The advantageousness of the combination of components (a) and (b) is present when the agent is used, i. in the washing or cleaning fleet. The washing or cleaning liquor is understood to mean the use solution containing the washing or cleaning agent which acts on textiles or fabrics (wash liquor) or hard surfaces (cleaning liquor) and thus comes into contact with the soiling present on textiles or fabrics or hard surfaces , Usually, the washing or cleaning liquor arises when the washing or cleaning process begins and the detergent or cleaning agent, for example, in a washing machine or other suitable container dissolved in water or diluted with water.

Hydrolytic enzymes in the sense of component (a) are proteases. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsværd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather ® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. The proteases are also used with particular preference Bacillus gibsonii and Bacillus pumilus disclosed in international patent applications WO2008 / 086916 and WO2007 / 131656 ,

Furthermore, within the scope of the invention, the enzymes may be formulated together with accompanying substances, for example from the fermentation or with stabilizers.

Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis. These include, in particular, the already mentioned commercial products Everlase and Purafect® OxP as examples of such proteases.

Agents used in a method according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-8 to 5 percent by weight based on active protein. Preferably, the enzymes are from 0.001 to 5% by weight, more preferably from 0.01 to 5% by weight, even more preferably from 0.05 to 4% by weight and most preferably from 0.075 to 3.5% by weight. % contained in these agents, wherein each enzyme contained can be present in the stated amounts.

The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).

The hydrolytic enzyme, at least one of which is present in a detergent or cleaning agent used in the method according to the invention (namely as component (a)), supports the cleaning performance of the composition with respect to certain soils or stains. Particularly preferably, an agent used in a method according to the invention contains a plurality of enzymes, wherein the enzymes may belong to the same or different enzyme classes. Most preferably, the enzymes exhibit synergistic effects on their action against certain soils or stains, i. the enzymes contained in the middle composition mutually support each other in their cleaning performance.

Synergistic effects can not only be present between different enzymes, but in particular also occur between one or more enzymes and other ingredients of the agent used in methods according to the invention. According to the invention, a hydrolytic enzyme (a) is combined therewith with a component (b), ie at least one substance which, in conjunction with the hydrolytic enzyme (a), produces a synergistic cleaning performance when the agent is used and which is a polyanionic substance.

These substances carry several negative charges. It is preferably a polymer having at least one negatively charged monomer, preferably having a plurality of negatively charged monomers. According to the invention, this polymer is therefore a negatively charged polymer. For example, polymers of organic acids or their salts, in particular polyacrylates and / or poly-sugar acids and / or polyarcylate copolymers and / or poly-sugar copolymers, are preferred. In this regard, further preferred compounds are polyacrylic sulfonates or polycarboxylates and their salts, copolymers or salts of the copolymers.

Examples of particularly preferable substances to be used are Acusol 587D (polyacrylic sulfonate, Rohm & Haas / Dow Chemical Company), Acusol 445N (polycarboxylate sodium salt, Rohm & Haas / Dow Chemical Company), Acusol 590 (polyacrylate copolymer; Rohm & Haas / Dow Chemical ), Acusol 916 (polyarcrylate sodium salt, Rohm & Haas / Dow Chemical Company), Sokalan CP42 (modified polycarboxylate sodium salt, BASF Company), Sokalan PA 30CL (polycarboxylate sodium salt, BASF Company), Dequest P 9000 (polymaleic acid, Thermphos Company), alginic acid , Poly-2-acrylamido-2-methyl-1-propane-sulfonic acid, poly-4-styrene sulfonic acid-co-maleic acid sodium salt, poly-acrylamido-co-acrylic acid sodium salt, poly-methacrylic acid sodium salt, poly-methyl vinyl ether-alt maleic acid or polyvinylsulfonic acid sodium salt.

• R1 ist H, -R, -NO₂, -CN, -halo, -N₃, -C1-8 alkyl, -(CH₂)nCO₂R2, -C2-8 alkenyl-CO₂R2, - O(CH₂)nCO₂R2, -C(O)NR2R3, -P(O)(OR2)₂, alkyl substitutiertes tetrazol-5-yl, -(CH₂)nO(CH₂)n aryl, -NR2R3, -(CH₂)n OR2, -(CH₂)n SR2, -N(R2)C(O)R3, -S(O₂)NR2R3, -N(R2)S(O₂)R3, -(CHR2)n NR2R3, -C(O)R3, (CH₂)n N(R3)C(O)R3, -N(R2)CR2R3 substitutiertes oder nicht substitutiertes (CH₂)n-cycloalkyl, substitutiertes oder nicht substitutiertes (CH₂)n-phenyl, oder zyklus;
• R2 ist H, -halo, -alkyl, -haloalkyl, -(CH₂)n-phenyl, -(CH₂)1-3-biphenyl, -(CH₂)1-4-Ph-N(SO₂-C1-2-alkyl)₂, -CO(CHR1)n-OR1, -(CHR1)n-Heterozyklus, -(CHR1)n-NH-CO-R1, - (CHR1)n-NH--SO₂R1, -(CHR1)n-Ph-N(SO₂-C1-2-alkyl)₂, -(CHR1)n-C(O)(CHR1)-NHR1, - (CHR1)n-C(S)(CHR1)-NHR1, -(CH₂)nO(CH₂)nCH₃, -CF₃, -C2-5 acyl, -(CHR1)nOH, - (CHR1)nCO₂R1, -(CHR1)n--O-alkyl, -(CHR1)n-O-(CH₂)n-O-alkyl, -(CHR1)n-S-alkyl, - (CHR1)n-S(O)-alkyl, -(CHR1)n-S(O₂)-alkyl, -(CHR1)n-S(O₂)-NHR3, -(CHR3)n-N₃, - (CHR3)nNHR4, 2 bis 8 Kohlenstoffatom Alken-Kette mit 1 bis 5 Doppelbindungen, 2 bis 8 Kohlenstoff Alkyne-Kette mit 1 bis 5 Dreifachbindungen, substitutierter oder nicht substitutierter -(CHR3)n Heterocyclus, oder substitutiertes oder nicht substitutiertes gesättigtes oder nicht gesättigtes -(CHR3)n Cycloalkyl;
• Wobei n größer als 1 ist und R1 und R3 gleich oder unterschiedlich sein kann;
• R3 ist H, -OH, -CN, substitutiertes Alkyl, -C2-8 alkenyl, substitutiertes oder nicht substitutiertes Zykloalkyl, -N(R1)R2, oder 5-6 Kohlenstoff gesättigter oder nicht gesättigter Heterozyklus. -NR2R3 kann bestehen aus einem gesättigten oder nicht gesättigten Heterozyklus oder einem Heterobizyklus von 4 to 7 Atomen;
• n ist 0-4 ;
• R4 und R5 besteht jeweils aus: H, -(CH₂)nOH, -C(O)OR6, -C(O)SR6, -(CH₂)n C(O)NR7R8, -O-C(O)-O-R7, einer Aminosäure oder einem Peptid;
• R6 ist H,
• R7 ist, -C(R7)(R8)-(CH₂)n-O-C(O)-R9, -(CH₂)n--C(R7)(R8)--O--C(O)R9, -(CH₂)n-C(R7)(R8)-O-C(O)-O-R9, or -C(R7)(R8)-(CH₂)n-O-C(O)-O-R9; und
• R7, R8 und R9 bestehen jeweils aus H, Alkyl, substitutiertes Alkyl, Aryl, substitutiertes Aryl, Alkenyl, substitutiertes Alkenyl, Alkynyl, substitutiertes Alkynyl, Heterozyklus, substitutiertes Heterozyklus, Alkylaryl, substitutiertes Alkylaryl, Zykloalkyl, substituiertes Zykloalkyl, oder CH₂CO₂alkyl.

Also usable according to the invention as component (b) are derivatives of the abovementioned substances. For the purposes of the present application, a derivative is understood as meaning a substance which is chemically modified starting from one of the abovementioned substances, for example by the conversion of a side chain or by covalent bonding of another compound to the substance. Such a compound may be, for example, low molecular weight compounds such as lipids or mono-, oligo- or polysaccharides or amines or amine compounds. Further, the substance may be glycosylated, hydrolyzed, oxidized, N-methylated, N-formylated, N-acetylated or methyl, formyl, ethyl, acetyl, t-butyl, anisyl, benzyl, trifluoroacetyl, N-hydroxysuccinimides, t-butyloxycarbonyl, benzoyl , 4-methylbenzyl, thioanizyl, thiocresyl, benzyloxymethyl, 4-nitrophenyl, benzyloxycarbonyl, 2-nitrobenzoyl, 2-nitrophenylsulphenyl, 4-toluenesulphonyl, pentafluorophenyl, diphenylmethyl, 2-chlorobenzyloxycarbonyl, 2,4,5-trichlorophenyl, 2-bromobenzyloxycarbonyl, 9 Fluoroenylmethyloxycarbonyl, tripheylmethyl, 2,2,5,7,8-pentamethylchroman-6-sulphonyl. Likewise, a derivative is to be understood as meaning the covalent or noncovalent binding of the substance to a macromolecular carrier, as well as noncovalent inclusion in suitable macromolecular cage structures. Also, couplings with other macromolecular compounds, such as polyethylene glycol, can be made be. Further preferred chemical modifications in the substances which can be used as component (b) are the modification of one or more of the chemical groups -COOH, -OH, NHNH, -NH ₂ -SH to -COOR, -OR, -NHR, -NR 2, -NHR, -NR, -SR; in which:
R is -CH = CH-R2, -C≡C-R2, -C (R ₂ ) = CH ₂ , -C (R ₂ ) = C (R 3), -CH = NR ₂ , -C (R ₂ ) = N-R 3 , a 4-7 C-ring system with or without substitution, 4-7 nitrogen heterocycle with or without substitution, or a 2 to 8 carbon chain with 1 to 5 double or triple bonds with substitutions selected from R1, R2, or R3;

• R 1 is H, -R, -NO ₂ , -CN, -halo, -N ₃ , -C 1-8 alkyl, - (CH ₂ ) n CO ₂ R ₂ , -C ₂ -8 alkenyl-CO ₂ R ₂ O, -O (CH ₂ ) nCO ₂ R ₂ , -C (O) NR ₂ R 3, -P (O) (OR ₂ ) ₂ , alkyl substituted tetrazol-5-yl, - (CH ₂ ) n O (CH ₂ ) n aryl, -NR ₂ R 3, - (CH ₂₎ n OR 2, - (CH ₂₎ n SR2, -N (R2) C (O) R3, -S (O ₂₎ NR2R3, -N (R2) S (O ₂₎ R 3, - (CHR 2) n NR2R3 , -C (O) R 3, (CH ₂ ) n, N (R 3) C (O) R 3, -N (R ₂ ) CR ₂ R 3, substituted or unsubstituted (CH ₂ ) n -cycloalkyl, substituted or unsubstituted (CH ₂ ) n -phenyl, or cycle;
• R2 is H, halo, alkyl, haloalkyl, - (CH ₂₎ n-phenyl, - _(CH2) 1-3-biphenyl, - (CH ₂₎ 1-4-Ph-N (SO ₂ -C 1 -2-alkyl) _2, -CO (CHR1) n OR1, - (CHR1) n-heterocycle, - (CHR1) n-NH-CO-R1, - (CHR1) n-NH - _SO2 R1, - (CHR1) n-Ph-N _(SO2 -C1-2 alkyl) _2, - (CHR1) n C (O) (CHR1) -NHR1, - (CHR1) n C (S) (CHR1) -NHR1, - ( CH ₂ ) nO (CH ₂ ) n CH ₃ , -CF ₃ , -C 2 5 acyl, - (CHR 1) n OH, - (CHR 1) n CO ₂ R ₁ , - (CHR 1) n --O-alkyl, - (CHR 1) O- (CH ₂₎ n O-alkyl, - (CHR1) n-alkyl, - (CHR1) n S (O) -alkyl, - (CHR1) n S (O ₂₎ -alkyl, - (CHR1) n S (O ₂₎ -NHR3, - (CHR 3) n N _3, - (CHR 3) nNHR4, 2 to 8 carbon atom alkene chain with 1 to 5 double bonds, from 2 to 8 carbon alkynes chain having 1 to 5 triple bonds, substitutierter or not substitutierter - (CHR 3) n heterocycle, or substituted or unsubstituted saturated or unsaturated - (CHR 3) n cycloalkyl;
• Where n is greater than 1 and R1 and R3 may be the same or different;
• R3 is H, -OH, -CN, substituted alkyl, -C2-8 alkenyl, substituted or unsubstituted cycloalkyl, -N (R1) R2, or 5-6 carbon saturated or unsaturated heterocycle. -NR 2 R 3 may consist of a saturated or unsaturated heterocycle or a heterocycle of 4 to 7 atoms;
• n is 0-4;
• R 4 and R 5 are each: H, - (CH ₂ ) n OH, -C (O) OR 6, -C (O) SR 6, - (CH ₂ ) n C (O) NR 7 R 8, -OC (O) -O- R7, an amino acid or a peptide;
• R6 is H,
• R 7 is -C (R 7) (R 8) - (CH ₂ ) n OC (O) -R 9, - (CH ₂ ) n -C (R 7) (R 8) - O - C (O) R 9, - (CH ₂ ) n C (R 7) (R 8) -OC (O) -O-R 9, or -C (R 7) (R 8) - (CH ₂ ) n OC (O) -O-R 9; and
• R7, R8 and R9 are each H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heterocycle, substituted heterocycle, alkylaryl, substituted alkylaryl, cycloalkyl, substituted cycloalkyl, or CH ₂ CO ₂ alkyl.

According to the invention, it is further possible to use all possible combinations of the abovementioned substances and / or their derivatives in processes according to the invention.

Preferably component (b) is added to the detergent or cleaning agent as a separate single substance, i. not as a component of another ingredient of the washing or cleaning agent. Preferably, component (b) is therefore free in the detergent, i. it is distributed in this and distributed as homogeneously as possible. In the case of liquid or gel detergents or cleaners, component (b) is preferably dissolved or dispersed in them. The washing or cleaning agent particularly preferably does not contain component (b) as part of the dosage form of the hydrolytic enzyme (a), in particular not as a constituent of an enzyme granulate.

According to the invention, liquid or gel-shaped, i. non-solid detergents or cleaners.

• Blut-Milch/Tusche auf Baumwolle: Produkt Nr. C5 von CFT B.V. Vlaardingen, Holland
• Voll-Ei/Pigment auf Baumwolle: Produkt Nr. 10N erhältlich von der Firma wfk Testgewebe GmbH; Brüggen-Bracht, Deutschland, in kleine Stücke geschnitten
• Schokolade-Milch/Tusche auf Baumwolle: Produkt Nr. C3 von CFT B.V. Vlaardingen, Holland
• Erdnuss Öl-Pigment/Tusche auf Polyester/Baumwolle: Produkt Nr. PC10 von CFT B.V. Vlaardingen, Holland
• Gras auf Baumwolle: Produkt Nr. 164 von erhältlich von der Firma Eidgenössische Material- und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Schweiz
• Kakao auf Baumwolle: Produkt Nr. 112 von erhältlich von der Firma Eidgenössische Material-und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Schweiz,

A synergistic cleaning performance of component (b) which, in conjunction with the hydrolytic enzyme (a), produces a synergistic cleaning performance using the agent is determined in a washing system which contains a detergent in a dosage between 4.5 and 7.0 grams per Liter wash liquor and the hydrolytic enzyme (a) and the component (b) each individually or in combination, wherein the enzyme is used in each case the same activity, the component (b) is used in a concentration of 0.00025 to 0.6 wt. %, in particular from 0.0003 to 0.5% by weight (use concentration in the wash liquor), and the washing performance against one or more of the stains blood milk / ink on cotton, full egg / pigment on cotton, chocolate Milk / ink on cotton, peanut oil pigment / ink on polyester / cotton, grass on cotton and cocoa on cotton, especially against one or more of the stains

• Blood milk / ink on cotton: Product No. C5 from CFT BV Vlaardingen, Holland
• Full egg / pigment on cotton: Product No. 10N available from the company wfk Testgewebe GmbH; Brüggen-Bracht, Germany, cut into small pieces
• Chocolate milk / ink on cotton: Product No. C3 from CFT BV Vlaardingen, Holland
• Peanut oil pigment / ink on polyester / cotton: Product No. PC10 from CFT BV Vlaardingen, Holland
• Grass on cotton: Product No. 164 from available from the company Eidgenössische Material- und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Switzerland
• Cocoa on cotton: Product No. 112 from available from the company Eidgenössische Material und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Switzerland,

is determined by measuring the whiteness of the washed textiles, the washing process for at least 30 minutes, optionally 60 minutes, carried out at a temperature of 20 ° C and the water has a water hardness between 15.5 and 16.5 ° (German hardness).

A preferred liquid detergent for such a washing system is composed as follows (all figures in weight percent): 0.3- 0.5% xanthan gum, 0.2-0.4% anti-foaming agent, 6-7% glycerol, 0.3-0.5% ethanol, 4-7% FAEOS (fatty alcohol ether sulfate), 24-28% nonionic surfactants, 1% boric acid, 1-2% sodium citrate (dihydrate), 2-4% soda, 14-16% coconut Fatty acids, 0.5% HEDP (1-hydroxyethane- (1,1-di-phosphonic acid)), 0-0.4% PVP (polyvinylpyrrolidone), 0-0.05% optical brightener, 0-0.001% dye, Rest demineralized water. Preferably, the dosage of the liquid detergent is between 4.5 and 5.5 grams per liter of wash liquor, for example, 4.9 grams per liter of wash liquor. Preference is given to washing in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.

A preferred powdered detergent for such a washing system is composed as follows (all figures in weight percent): 10% linear alkylbenzenesulfonate (sodium salt), 1.5% C12-C18 fatty alcohol sulfate (sodium salt), 2.0% C12-C18 fatty alcohol with 7 EO, 20% sodium carbonate, 6.5% sodium bicarbonate, 4.0% amorphous sodium disilicate, 17% sodium carbonate peroxohydrate, 4.0% TAED, 3.0% polyacrylate, 1.0% carboxymethyl cellulose, 1.0% phosphonate, 25% sodium sulfate, balance: optional foam inhibitors, optical brightener, fragrances and, if necessary, water ad 100%. Preferably, the dosage of the liquid detergent is between 6.0 and 7.0 grams per liter of wash liquor, for example, 6.7 grams per liter of wash liquor. Preference is given to washing in a pH range between pH 9 and pH 11.

Preferably, a liquid detergent is used.

The degree of whiteness, i. the brightening of the stains, is preferably determined by optical measuring methods, preferably photometrically. A suitable device for this purpose is for example the spectrometer Minolta CM508d. Usually, the devices used for the measurement are previously calibrated with a white standard, preferably a supplied white standard.

The activity-like use ensures that, even if the ratio of active substance to total protein (the values of the specific activity) diverge, the respective enzymatic properties, for example the washing performance of certain soils, are compared. In general, a low specific activity can be compensated by adding a larger amount of protein. Methods for the determination of the enzyme activities are familiar to the expert in the field of enzyme technology and are routinely used by him. For example Method for determining protease activity disclosed in Tenside, Vol. 7 (1970), pp. 125-132 , The protease activity is preferably indicated in PE (protease units). For example, suitable protease activities are 5 or 10 PE (protease units) per ml wash liquor. However, the enzymatic activity used is not equal to zero.

Preferably, the synergistic cleaning performance is based on a novel mechanism of action, i. There is no increase in the enzyme activity per se in the classical sense, as they would - in terms of proteases - would be measured in one of the following methods. Accordingly, a synergism according to the invention is also present in particular if an improved cleaning performance in the presence of components (a) and (b) is found compared to the sum of the cleaning powers of component (a) alone and component (b) alone, and the component (b) in at least one of the subsequent test methods, preferably in both subsequent test methods, has no effect of increasing the hydrolytic activity of component (a), in particular with regard to increasing the hydrolytic activity of a protease, beyond the standard measurement error:

Method 1

The protease activity is determined quantitatively by the release of the chromophore para-nitroaniline (pNA) from the substrate. The substrate is: suc-L-Ala-L-Ala-L-Pro-L-Phe-p-Nitroanilide (substrate solution: 110 mM in DMSO). The protease cleaves the substrate and releases pNA. The release of pNA causes an increase in absorbance at 410 nm, the time course of which is a measure of enzymatic activity (see Del Mar et al., 1979).

The measurement is carried out at a temperature of 25 ° C, at pH 8.6 and a wavelength of 410 nm. The measurement time is 5 min and the measurement interval 20s to 60s.

The use buffer (Tris-HCl pH 8.6) is used as a blank sample, 10 μL of the substrate solution are added to each cuvette, 1000 μL of buffer are added to each cuvette, 1-300 μl of buffer (s) are added Add component (b) (0.1, 0.2, 0.5 or 1% by weight in working buffer) to the cuvette and place 1-300 μl of the protease or blank sample in the cuvette The measurement is started by mixing the sample After mixing, the cuvettes are immediately transferred to the photometer and the measurement is started.An activation or stabilization of the protease can be quantified by means of the measurement data.

Method 2

Protease activity is determined via the hydrolysis of casein and subsequent reaction of TCA-soluble peptides with Folin &Ciocalteu's phenol reagent. The absorbance of the resulting complex is measured at 660 nm and compared to a tyrosine standard.

Reaction mixtures contain 3 ml of 0.8% (w / v) casein and 0.5 ml of a suitable enzyme dilution with or without the component (b) to be tested (concentration 0.1, 0.2, 0.5 or 1 wt. %), both in universal buffer 1 from Britton and Robinson, pH 9.5 (see J. Chem. Soc., 1931, p 1451). The mixtures are incubated for 30 minutes at 25 ° C, then the reaction is stopped by adding Stop Reagent (TCA). In control reactions, the stop reagent is added before enzyme addition with or without the substance to be tested. After 20 minutes at 25 ° C, the reaction mixtures are filtered through Whatman # 42 filter paper or centrifuged.

To the filtrate is added water, sodium carbonate and Folin &Ciocalteu's phenol reagent. After 30 minutes of incubation, the absorbance at 660 nm is determined. Similarly, an aliquoted portion of 200 μl of a tyrosine standard is determined. The activity is expressed in protease units, with 1 PE defined as the amount of proteolytic enzyme resulting in the release of 1 mmol tyrosine released per minute under defined conditions (cf. Anson, ML, (1938) J. Gen. Physiol. 22, 79-89 such as Folin, O., and Ciocalteu, V., (1929) J. Biol. Chem. 73, 627 ).

In a further embodiment of the invention, the method is characterized in that the substances used as component (b) have specific molecular weights. In a further embodiment of the invention, the method is therefore characterized in that this component has a molecular weight (MW) from 150 to 5x10 ⁶ daltons, in particular from 200 to 1x10 ⁶ daltons, from 220 to 0,75x10 ⁶ Dalton and in particular from 400 to 0.5x10 ⁶ daltons. For substances with such molecular weights, particularly advantageous synergistic cleaning results in conjunction with the hydrolytic enzyme (component (a)).

Advantageous synergistic cleaning performances are also obtained by the fact that the substance used as component (b) is present in a certain concentration in the washing or cleaning agent. In a further embodiment of the invention, the method is characterized in that this component is present in the composition in a concentration of 0.15 to 50 wt .-%, in particular from 0.9 to 30 wt .-%.

With regard to the use concentration, ie the concentration in the washing or cleaning liquor, a particularly advantageous synergistic cleaning performance also results from the fact that the substance used as component (b) is present in a certain concentration in the washing or cleaning liquor. In a further embodiment of the invention, the method is therefore characterized in that this component in the washing or cleaning liquor is present in a concentration of 0.00025 to 0.6 wt .-%, in particular from 0.0003 to 0.5 wt .-%.

Detergents and cleaning agents which can be used in the process according to the invention include all conceivable types of detergents or cleaners, both concentrates and undiluted agents, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include detergents for textiles, carpets, or natural fibers, for which the term detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, ie in addition to manual and machine Dishwashing agents, for example, scouring agents, glass cleaners, toilet scenters, etc. The washing and cleaning agents in the invention also include washing aids which are added to the actual detergent in the manual or machine textile laundry to achieve a further effect. Furthermore, laundry detergents and cleaners in the context of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example to dissolve stubborn soiling, and also agents which are in one of the actual Textile laundry downstream step to give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Among the latter, i.a. calculated the fabric softener.

The detergents or cleaning agents which can be used in the process according to the invention, which can be in the form of homogeneous solutions or suspensions, in particular in powdered solids, can in addition to the active compounds used according to the invention - the components (a) and (b) - in principle all known and contain usual ingredients in such agents, wherein preferably at least one further ingredient is present in the agent. The agents may, in particular, builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, grayness inhibitors, foam regulators and dyes and perfumes and Combinations of these included. In particular, a further combination of the active compounds according to the invention with one or more further ingredient (s) of the agents proves advantageous, since then a further improved cleaning performance can be achieved by further resulting synergisms. In particular, the combination with a surfactant and / or a builder and / or a bleaching agent such a further synergism is achieved. Such preferred others Ingredients of the detergent or cleaning agent are disclosed in the international publication WO 2009/021867 , whose disclosure is therefore expressly referred to or the disclosure thereof is therefore expressly incorporated into the present application.

The ingredients to be selected as well as the conditions under which the agent is used, such as temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the respective cleaning problem. Thus, conventional temperatures for the use of detergents and cleaners in the ranges of 10 ° C over 40 ° C and 60 ° C up to 95 ° for mechanical means or in technical applications. Preferably, the ingredients of the respective agents are coordinated, in particular in such a way that synergies arise with regard to the cleaning performance. Synergies are particularly preferred which are in a temperature range from 10 ° C to 30 ° C, from 15 ° C to 30 ° C from 10 ° C to 25 ° C, from 15 ° C to 25 ° C and most preferably at 20 ° C are present.

In another preferred embodiment, an agent useful in the method of the invention further contains the hydrolytic enzyme in an amount of from 2 μg to 20 mg, preferably from 5 μg to 17.5 mg, more preferably from 20 μg to 15 mg and most preferably from 50 μg to 10 mg per g of the agent. Further, the hydrolytic enzyme contained in the agent, in particular a protease, and / or other ingredients of the agent may be coated with a substance impermeable to the enzyme at room temperature or in the absence of water, which becomes permeable to the enzyme under conditions of use of the agent. Such an embodiment of the invention is thus characterized in that the hydrolytic enzyme is coated with a substance which is impermeable to the enzyme at room temperature or in the absence of water. Furthermore, the washing or cleaning agent itself may be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process.

1. (a) in fester Form vorliegt, insbesondere als rieselfähiges Pulver mit einem Schüttgewicht von 300 g/l bis 1200 g/l, insbesondere 500 g/l bis 900 g/l, oder
2. (b) in pastöser oder in flüssiger Form vorliegt, und/oder
3. (c) als Einkomponentensystem vorliegt, oder
4. (d) in mehrere Komponenten aufgeteilt ist.

In further embodiments of the invention, the method is characterized in that the washing or cleaning agent

1. (A) is in solid form, in particular as a free-flowing powder having a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l, or
2. (b) is in pasty or liquid form, and / or
3. (c) is present as a one-component system, or
4. (d) is divided into several components.

These embodiments of the present invention further include all solid, powdered, liquid, gel or pasty dosage forms of the method according to the invention usable means, which may optionally consist of several phases and may be present in compressed or uncompressed form. The agent can be present as a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l. The solid dosage forms of the composition also include extrudates, granules, tablets or pouches. Alternatively, the agent can also be liquid, gelatinous or pasty, for example in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste. Furthermore, the agent may be present as a one-component system. Such means preferably consist of one phase. Alternatively, an agent can also consist of several phases. Such an agent is therefore divided into several components.

Detergents or cleaning agents which can be used in the process according to the invention may contain only one protease. Alternatively, however, they may also contain further hydrolytic enzymes or other enzymes in a concentration which is expedient for the effectiveness of the agent, it being possible in principle to use all enzymes established for this purpose in the prior art. As other enzymes preferably used are all enzymes that can develop catalytic activity in the agent, in particular amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, β-glucosidases, carrageenases, oxidases, perhydrolases, oxidoreductases or lipases, and preferably their mixtures. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.
The use described herein is advantageous for eliminating contaminants from textiles or hard surfaces, particularly proteinaceous contaminants. Embodiments of this subject invention include, for example, hand washing, manual removal of stains from textiles or from hard surfaces or machine processes.

The uses in processes for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent , The same applies to methods for cleaning hard surfaces.

Since a hydrolytic enzyme, ie component (a), already naturally possesses a hydrolytic activity and also unfolds this in media which otherwise have no cleaning power, such as, for example, in mere buffer, such a method may also merely consist in that apart from the added component (b) the only further component is a hydrolytic enzyme, ie component (a) is applied, preferably in a buffer solution or in water. This represents a further embodiment of this subject of the invention.

All uses according to the invention in such processes are carried out in a temperature range from 10 ° C. to 30 ° C. A synergistic interaction of the components (a) and (b) with regard to the cleaning performance is especially at these lower to middle washing temperatures or cleaning temperatures.

In a further embodiment, the use is characterized in that component (b) is present in the agent from 0.15 to 50% by weight, in particular from 0.9 to 30% by weight.

As described above, this component (component (b)) advantageously, in particular synergistically, cooperates with a hydrolytic enzyme (component (a)), so that not only the cleaning performance of a washing or cleaning agent (or the wash liquor formed by this agent) is improved, but also the cleaning performance of the hydrolytic Enyzms itself.

Preferred embodiments of uses according to the invention are further characterized in that the substances used as component (b) have specific molecular weights. In preferred embodiments, the invention provides a use according to the invention therefore is characterized in that this component has a molecular weight (MW) from 150 to 5x10 ⁶ daltons, in particular from 200 to 1x10 ⁶ daltons, from 220 to 0,75x10 ⁶ Dalton and in particular from 400 to 0.5x10 ⁶ daltons.

Examples: example 1

To determine the washing performance, the following formulation was used for a laundry detergent (see Table 2). Table 2: ingredient Wt .-% pure substance xanthan 0.3-0.5 Anti-foaming agents 0.2-0.4 glycerin 6-7 ethanol 0.3-0.5 FAEOS 4-7 Nonionic surfactants (FAEO, APG, etc.) 24 - 28 boric acid 1 Sodium citrate (dihydrate) 1-2 soda 2-4 Coconut fatty acids 14-16 HEDP 0.5 PVP 0-0.4 Optical brighteners 0-0.05 dye 0 to 0.001 Perfume 0-2 H ₂ O, demineralized rest

Assays were assembled into 24-well plates in 1 ml each of wash liquor as shown in Table 3 below. The incubation was carried out for 60 minutes at 20 ° C with shaking (about 100 revolutions per minute (rpm)). Table 3: volumes solution 420 μl 161-966 mg of laundry detergent in 42 ml of water or buffer 30-530 μl 1-100 PE / ml protease 30-530 μl Prepared substance solution rest H ₂ O Soiling ∅ approx. 1cm

• Blut-Milch/Tusche auf Baumwolle: Produkt Nr. C5 von CFT B.V. Vlaardingen, Holland Voll-Ei/Pigment auf Baumwolle: Produkt Nr. 10N erhältlich von der Firma wfk Testgewebe GmbH; Brüggen-Bracht, Deutschland,
• Schokolade-Milch/Tusche auf Baumwolle: Produkt Nr. C3 von CFT B.V. Vlaardingen, Holland Erdnuss Öl-Pigment/Tusche auf Polyester/Baumwolle: Produkt Nr. PC10 von CFT B.V. Viaardingen, Holland
• Gras auf Baumwolle: Produkt Nr. 164 von erhältlich von der Firma Eidgenössische Material- und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Schweiz
• Kakao auf Baumwolle: Produkt Nr. 112 von erhältlich von der Firma Eidgenössische Material- und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Schweiz.

Round pieces of stains (diameter approx. 10 mm) were used, which were selected from the following stains:

• Blood milk / ink on cotton: Product No. C5 from CFT BV Vlaardingen, Holland Whole egg / pigment on cotton: Product No. 10N available from the company wfk Testgewebe GmbH; Bruggen-Bracht, Germany,
• Chocolate milk / ink on cotton: Product No. C3 from CFT BV Vlaardingen, Holland Peanut oil pigment / ink on polyester / cotton: Product No. PC10 from CFT BV Viaardingen, The Netherlands
• Grass on cotton: Product No. 164 from available from the company Eidgenössische Material- und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Switzerland
• Cocoa on cotton: Product No. 112 from available from the company Eidgenössische Material- und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen, Switzerland.

After incubation, the soils were rinsed, dried and fixed three times and the whiteness of the washed fabrics was measured as compared to a white standard (d / 8, 8mm, SCI / SCE) normalized to 100% (determination of L-value). , The measurement was carried out on a colorimeter (Minolta Cm508d) with an illumination setting of 10 ° / D65.

Proteases used were the alkaline protease from Bacillus lentus DSM 5483 ( WO 92/21760 , hereinafter referred to as Protease 1) as well as the protease which are shown in FIG. 2 or SEQ ID NO. 3 of the international publication WO 03/057713 (hereinafter referred to as Protease 2).

Example 2

• Acusol 590 (Polyacrylat-Copolymer, Rohm & Haas/Dow Chemical)
• Sokalan PA 30CL (Polycarboxylat Natriumsalz, BASF)
• Poly-2-acrylamido-2-methyl-1-propan-sulfonsäure
• Poly-4-styrolsulfonsäure-co-maleinsäure Natriumsalz
• Poly-acrylamido-co-acrylsäure Natriumsalz
• Poly-methacrylsäure Natriumsalz
• Poly-vinylsulfonsäure Natriumsalz
• Polyacrylat Natriumsalz

The washing performance was tested with the following substances (component (b)):

• Acusol 590 (polyacrylate copolymer, Rohm & Haas / Dow Chemical)
• Sokalan PA 30CL (polycarboxylate sodium salt, BASF)
• Poly-2-acrylamido-2-methyl-1-propane-sulfonic acid
• Poly-4-styrenesulfonic acid-co-maleic acid sodium salt
• Poly-acrylamido-co-acrylic acid sodium salt
• Poly-methacrylic acid sodium salt
• Polyvinyl sulfonic acid sodium salt
• Polyacrylate sodium salt

Stock solutions of these substances were prepared with 0.00001-1.5 M substance or 0.0001-55% (weight or volume) in water or buffer (phosphate 0.00001-1.5 M pH 6.5-8.0 or Tris 0.00001-1.5 M pH 7.5-9.0 or Soerensen buffer pH 7.5-9.0 or citrate buffer 0.00001-1.5 M pH 4.5-7.0 or acetate Buffer 0.00001-1.5 M pH 2.5-5.5).

The following Tables 4 and 5 show the resulting cleaning performance for each given experimental approaches. The results obtained are the sum of the improvements over all six specified soils and are given as percent power, with the difference of the remission values from the detergent investigated minus the control (detergents without enzyme and no substance) being formed for each value. The increase in performance of the detergent with hydrolytic enzyme (in this case with protease), but without performance-enhancing substance, compared to the detergent without hydrolytic enzyme (protease) and substance was normalized to 100% as a reference. 100% therefore represent the cleaning performance of the detergent with hydrolytic enzyme (protease) alone, ie without performance-enhancing substance. Values greater than 100%, however, therefore show an increased cleaning performance compared to this reference, values less than 100% reduced Cleaning performance against this reference. The values specified in the tables as "without enzyme" smaller than 100 therefore mean that a detergent comprising the respective substance, but not the hydrolytic enzyme, although a slightly better cleaning performance than the control, but by far not the cleaning performance of the reference detergent (With hydrolytic enzyme, without substance) and is far below the cleaning performance of a detergent with hydrolytic enzyme and performance-enhancing substance.

It is clear that the components used (b) cause a synergistic increase in the washing performance of those detergents containing a hydrolytic enzyme, namely a protease, ie component (a). In controls which do not contain a hydrolytic enzyme, these components (b) do not synergistically increase the washing performance, so that the enhanced washing performance is due to a beneficial synergistic interaction of components (a) and (b). Table 4: Wash at 20 ° C with Protease 1 substance 8% in the detergent 4% in the detergent 8% without enzyme Acusol 590 153.6% 150.0% 18% Sokalan PA 30CL 182.1% 167.9% 43% Polyacrylate sodium salt 157.1% 142.9% 21% Poly-methacrylic acid sodium salt 175.0% 150.0% 36% Poly-acrylamido-co-acrylic acid sodium salt 150.0% 139.3% 25% Polyvinyl sulfonic acid sodium salt 160.7% 125.0% 21% Poly-4-styrenesulfonic acid-co-maleic acid sodium salt 142.9% 132.1% 11% Poly-2-acrylamido-2-methyl-1-propane-sulfonic acid 146.4% 132.1% 18% Wash at 20 ° C with Protease 2 substance 8% in the detergent 4% in the detergent 8% without enzyme Polyacrylate sodium salt 138% 119% 23% Polyvinyl sulfonic acid sodium salt 135% 115% 23%

Advantageous increases in the cleaning performance of a protease-hydrolytic enzyme agent were also obtained in a comparable manner using the compounds Acusol 587D, Acusol 916, Sokalan CP42, alginic acid or poly-methyl vinyl ether-old maleic acid as component (b).

Claims (7)

1. The use of a polyanionic substance for achieving a synergistic enzyme-based cleaning performance in conjunction with a protease in a washing or cleaning agent during use of the washing or cleaning agent, characterized in that it is carried out in a temperature range of 10°C to 30°C.
2. The use according to claim 1, characterized in that the polyanionic substance is present in the agent at a concentration of from 0.15 to 50 wt.%, in particular from 0.9 to 30 wt.%.
3. The use according to claim 1 or 2, characterized in that the washing or cleaning agent contains protease in an amount of from 2 µg to 20 mg, preferably from 5 µg to 17.5 mg, particularly preferably from 20 µg to 15 mg, and very particularly preferably from 50 µg to 10 mg, per g of the agent, and/or in that protease in the washing or cleaning agent is encased by a substance that is impermeable to the enzyme at room temperature or in the absence of water.
4. The use according to one of claims 1 to 3, characterized in that the washing or cleaning agent

   (a) is present in solid form, in particular as a flowable powder having a bulk density of from 300 g/l to 1200 g/l, in particular from 500 g/l to 900 g/l, or

   (b) is present in pasty or liquid form, and/or

   (c) is present as a single-component system, or

   (d) is divided into a plurality of components.
5. The use of a polyanionic substance for increasing the enzyme-based cleaning performance of a protease in a washing or cleaning process, characterized in that it is carried out in a temperature range of from 10°C to 30°C.
6. The use according to one of claims 1 to 5, characterized in that the polyanionic substance has a molecular weight (MW) of from 150 to 5x10⁶ Dalton, in particular from 200 to 1x10⁶ Dalton, from 220 to 0.75x10⁶ Dalton, and in particular from 400 to 0.5x10⁶ Dalton.
7. The use according to one of claims 1 to 6, characterized in that the polyanionic substance is present in the washing or cleaning liquor at a concentration of from 0.00025 to 0.6 wt.%, in particular from 0.0003 to 0.5 wt.%.