WO1999028425A1 - Reinforcement of the cleaning effects of detergents through the use of cellulase - Google Patents

Abstract

According to the invention, the cleaning effects of textiles detergents on polysaccharide stains which do not usually consist solely of starch can be improved essentially through the use of cellulase.

Description

 REINFORCEMENT OF THE DETERGENT PERFORMANCE OF DETERGENTS BY THE

USE OF CELLULASE

The present invention relates to the use of cellulase to enhance the cleaning performance of detergents against starchy soiling.

Enzymes, especially proteases and lipases, but also amylases and cellulases, are used extensively in washing, auxiliary washing and cleaning agents. Proteases, lipases and amylases are primarily used to remove protein, fat and starch stains. In contrast, cellulases have a special position because they are not used to remove special stains, but because of their ability to break down cellulose, have long been known as anti-aging agents for cotton fabrics. A side effect of the breakdown of cellulose fibrils by cellulases is the deepening of the optical color impression, the so-called color refreshment, which results from the treatment of colored cotton textiles with cellulases when the undyed fibrils resulting from fiber damage and originating from the interior of the fiber are removed.

The enzymes mentioned are not only used individually, but usually in combinations with one another. For example, a detergent is known from European patent application EP 0 755 999 A1 which contains a stability-improved amylase in combination with protease, it being possible for further enzymes such as lipase and cellulase to be present. The international patent application WO 94/24258 AI relates to enzyme-containing detergents which contain protease, lipase, amylase and cellulase and not more than 10% by weight of surfactant and / or not more than 40% by weight of builder. European detergents EP 0 425 214 A2 disclose detergents which, in addition to surfactants and builders, contain protease and amylase and a third enzyme selected from lipase and cellulase. European patent application EP 0 365 103 A2 relates to detergents, the 4-30% by weight nonionic surfactant, 25-80% by weight builder, 1-15% by weight water and 0.1-2% by weight protease , 0.2-1 wt .-% cellulase and up to 2 wt .-% amylase. The problem with polysaccharide soiling is that naturally occurring polysaccharides, such as those found in foods, do not normally consist exclusively of starch, but also contain other or otherwise linked saccharides. While α-amylases intended for use in detergents are generally well suited to hydrolyzing the starch content of polysaccharide stains in water-soluble oligosaccharides, their dirt removal ability can be felt to be in need of improvement if they are stains from other polysaccharides or these make up larger parts of the polysaccharide stains.

The applicant had set itself the goal of remedying this situation and improving the cleaning performance of detergents compared to polysaccharide stains.

Surprisingly, it was found that this can be achieved by using an enzyme which has hitherto only been used for completely different purposes, namely cellulase.

The invention therefore relates to the use of cellulase to increase the cleaning performance of textile detergents against polysaccharide stains.

Further objects of the invention are the use of cellulase for removing polysaccharide stains on textiles and a method for removing polysaccharide stains on textiles by using celluase. In the context of the use according to the invention and the method according to the invention, the cellulase, alone or as a component of a laundry pretreatment agent, can be applied to textiles contaminated with polysaccharide stains in the sense of a pretreatment step before the laundry. However, the cellulase is preferably used as a constituent of an aqueous cleaning solution, which may additionally contain the usual ingredients of wash liquors. The cellulase is preferably used to enhance the cleaning performance of detergents which already contain an enzymatic active ingredient for starch removal, that is to say an α- or β-amylase. In these, the cellulase surprisingly enhances the amylolytic effect of the amylase, so that when using a combination of cellulase and amylase, a higher cleaning performance compared to polysaccharide additive Soiling results than would be expected from the use of the individual enzymes. The aqueous cleaning solution for use in the process according to the invention preferably also contains an amylase in addition to the cellulase used according to the invention.

Cellulase is preferably used in such amounts to increase the cleaning performance of laundry detergents against polysaccharide stains that the agent has cellulolytic activities in the range from 10 mU / g to 700 mU7g, in particular from 25 mU / g to 400 mU / g. When used to remove polysaccharide stains on textiles and in the context of the method according to the invention, an aqueous system is preferably used which has a cellulolytic activity in the range from 0.05 U / 1 to 2.5 U / 1, in particular from 0. 1 U / 1 to 1.5 U / 1. In the context of machine washing processes, for example the usual household washing using washing machines, the activity mentioned does not have to be maintained over the entire washing cycle in order to achieve the desired washing result, as long as it is ensured that at least for a short time, for example about 5 to 20 minutes a cellulolytic activity occurs in the range mentioned. The determination of cellulolytic activity (CMCase activity) is based on modifications by M. Lever in Anal. Biochem. 47 (1972), 273-279 and Anal. Biochem. ! 31_ (1977), 21-27. A 2.5 percent by weight solution of carboxymethyl cellulose (obtained from Sigma, C-5678) in 50 mM glycine buffer (pH 9.0) is used for this. 250 μl of this solution are incubated for 30 minutes at 40 ° C. with 250 μl of the enzyme solution to be tested. Then 1.5 ml of a 1 percent by weight solution of p-hydroxybenzoic acid hydrazide (PAHBAH) in 0.5 M NaOH, which contains 1 mM bismuth nitrate and 1 mM potassium sodium tartrate, are added and the solution is heated to 70 ° C. for 10 minutes. After cooling (2 minutes at 0 ° C), the absorption at 410 nm (for example using a Uvikon® 930 photometer) is determined against a blank value at room temperature. A solution is used as the blank value, which was prepared like the measurement solution, with the difference that both the PAHBAH solution and the CMC solution are added in this order only after the incubation of the enzyme and heated to 70.degree. In this way, possible activities of the cellulase with Media components also recorded in the blank value and subtracted from the total activity of the sample, so that in fact only the activity against CMC is determined. 1 U corresponds to the amount of enzyme that produces 1 μmol glucose per minute under these conditions.

Commercial cellulases such as KAC®, Celluzyme®, Carezyme® and / or the enzymes known from international patent applications WO 96/34108 or WO 97/13862 can be used. The cellulase can be used in particular in particulate compositions, as described for example in European patent EP 0 564 476 or in international patent applications WO 94/23005 for other enzymes, adsorbed on carrier substances and / or embedded in coating substances around them protect against premature inactivation.

Since the cleaning performance of amylolytic and cellulolytic enzymes increases unexpectedly when such enzymes are used together, a combination of cellulase and amylase is preferably used according to the invention. In these combinations, it is preferred to use an amylolytic activity in the range from about 10 U / g to about 150 U / g, in particular from about 15 U / g to about 120 U / g, to increase the cleaning performance of the detergent. The amylase activity is determined analogously to the standardized method described above for the cellulase activity using soluble starch instead of carboxymethyl cellulose at pH 5 (sodium acetate buffer) and 40 ° C. within 15 minutes. According to the invention, the ratio of cellulase to amylase activity, in each case expressed in U, is preferably in the range from 1:11,500 to 1:15, in particular 1:4500 to 1:40.

The detergents to be reinforced according to the invention in terms of their cleaning performance, which may be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can in principle contain all of the known ingredients customary in such agents, in addition to the cellulase used according to the invention. You can in particular builder substances, surface-active surfactants, bleaching agents based on organic and / or in particular inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators and or more Contain auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, and colorants and fragrances.

The agents can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants. Such surfactants are present in the detergents in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. Preferred surfactants of the sulfonate type are C - C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C] ₂ -C ₈ monoolefins with an end or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C] ₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof represent how they are obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. The alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C ₂₀ oxo alcohols and those Half-secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₂ -C ₆ alkyl sulfates and C] -C ₁₅ alkyl sulfates and C ₁₄ -Ci ₅ alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cπ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 1 -C ₈ -Fatty alcohols with 1 to 4 EO. Because of their high foaming behavior, they are normally only used in relatively small amounts in detergents, for example in amounts of 1 to 5% by weight. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Other anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methylglycine (sarcosides). The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. Soaps, for example in amounts of 0.2% by weight to 5% by weight, are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Anionic surfactants are contained in the agents to be improved in their cleaning performance preferably in amounts of 1% by weight to 30% by weight and in particular in amounts of 5% by weight to 25% by weight.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkyl phenols having 5 to 12 carbon atoms in the alkyl radical, can also be used.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the Alcohol residue may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C] -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -Cπ alcohols with 7 EO, Cι - Cis alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁ -Cι ₄ - alcohol with 3 EO and ₂ - cis alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R'CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

R ^

R -CO-N- [Z] (I) The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ⁴ -OR ⁵

I (II)

R ³ -CO-N- [Z]

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, Cj-C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest is available. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that ethoxylated fatty alcohols, especially not more than half of them. So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean “dimeric” in this way, but also correspondingly “trimeric” surfactants. Surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE 195 03 061. End group-blocked dimer and trimeric mixed ethers according to German patent application DE 195 13 391 itself i n especially by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.

An agent to be reinforced in its cleaning performance according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotronic acetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediamine ethylenediamine (methylenediamine), ethylenediamine ethylenediamine (methylenediamine), ethylene (methylenediamine), ethylene (methylenediamine), ethylenediamine ethylenediamine l-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially those by Oxidation of polysaccharides or dextrins accessible polycarboxylates of international patent application WO 93/16110 or international patent application WO 92/18542 or European patent EP 0 232 202, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerizable substances may contain copolymerized without carboxylic acid functionality. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case 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 proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and or an esterified vinyl alcohol or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers can be produced in particular by processes which are described in German patents DE 42 21 381 and DE 43 00 772, and generally have a relative molecular weight of between 1,000 and 200,000. Other preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts. Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing agents.

Particularly suitable water-soluble inorganic builder materials are alkali silicates and polymeric alkali phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. In particular, crystalline or amorphous alkali aluminum silicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular from 1% by weight to 5% by weight. %, used. Among them, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA), are preferred . Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a molar Na ₂ O: SiO ₂ ratio of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. Crystalline sheet silicates of the general formula Na ₂ Si _x O _{2x +} ι H ₂ O, in which x, the so-called modulus, is a number from 1.9 to 4, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicate (Na ₂ Si O y HO) are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 425 428 described, can be used. In a further preferred embodiment of such agents, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 294 753, are used in a further preferred embodiment of agents according to the invention. In a preferred embodiment of agents according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as is described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1. Builder substances are contained in detergents preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.

Suitable peroxygen compounds are in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate. Hydrogen peroxide can also be generated using an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. Alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or hydrogen peroxide are particularly preferably used in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. If a detergent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate may be useful.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxy-benzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin Ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN) , acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and or N-acylated lactams, for example N-benzoylcaprolactam, which are known from WO 94/294 from WO 94/2994 / 28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 19620267, which are known from German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, described in German patent application DE 196 05 688 Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, which are described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, the manganese known from European patent EP 0 392 592 , Iron, cobalt and copper complexes, the cobalt complexes known from the international patent applications WO 96/23859, WO 96/23860 and WO 96/23861 and or the European patent specification EP 0 443 651 or the European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

In addition to the cellulase essential to the invention and the abovementioned oxidase, the enzymes which can be used in the compositions are those from the class of proteases, lipases, cutinases, amylases, pullulanases, β-glucanases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example proteases such as Subtilisin BPN ', Properase®, BLAP®, Optimase®, Opticlean®, Maxatase®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym®, Everlase® and / or Purafect® G or OxP, amylases such as BAN® , Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. Enzymatic active ingredients obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia, are particularly suitable. These optionally additionally used enzymes can, as described for example in the European patent EP 0 564476 or in the international patent applications WO 94/23005, adsorbed on carriers and / or embedded in coating substances to prevent them from premature inactivation to protect. They are contained in detergents preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to enzymes stabilized against oxidative degradation, such as, for example, from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.

The organic solvents which can be used in the agents to be improved in their cleaning performance, in particular if they are in liquid or pasty form, include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 up to 4 carbon atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned. Such water-miscible solvents are preferably present in detergents in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

To set a desired pH value, which does not result from the mixture of the other components, the detergents can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not contained in detergents above 20% by weight, in particular from 1.2% by weight to 17% by weight.

Color transfer inhibitors suitable for use in agents to be improved in their cleaning performance according to the invention include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor. Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water-soluble, acidic groups containing polyamides are suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent, are preferably used .

Detergents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.

In particular when used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred. The preparation of solid agents of the type described above presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, the cellulase and, if appropriate, further enzymes and any other thermally sensitive ingredients, such as bleaching agents, optionally being added separately later. For the production of particulate agents with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1, a process known from European patent EP 0486 592 and having an extrusion step is preferred. A further preferred production using a granulation process is described in European patent EP 0 642 576. Liquid or pasty detergents in the form of solutions containing customary solvents are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

Examples

example 1

To determine the washing capacity, cotton fabric soiled with standardized test soiling (oatmeal / cocoa) was washed at 40 ° C (detergent dosage 76 g; water hardness 16 ° d; load 3.5 kg, short program) in a household washing machine (AEG Öko Lavamat® 694) washed. Table 1 below shows the washing results (in dE initial value minus dE after washing, measuring device Minolta® CR 310) for a cellulase- and amylase-free detergent VI, for a cellulase-free detergent V2 (containing 0.6% by weight of the amylase granulate Termamyl ® 60T; manufacturer Novo Nordisk) and for agents Ml to M5 reinforced according to the invention in their cleaning performance, which were otherwise composed like V2, but with 0.2% by weight, 0.4% by weight, 0.6% by weight. -%, 0.8% by weight or 1.0% by weight Celluzyme® 0.7T (manufacturer Novo Nordisk) had been added, as the result of duplicate determinations.

Table 1: Washing results (dE AW - dE washed)

It can be seen that the cleaning performance of the agents according to the invention are significantly superior to the agents according to the invention in terms of cleaning performance. Example 2

Example 1 was repeated, in the compositions with additives used according to the invention (M6 to MIO) instead of Celluzyme®, activity-equivalent amounts of KAC® 500 (manufacturer Kao) were used. From the washing results given in Table 2, one can also see here the superiority of the cleaning performance of the agents according to the invention.

Table 2: Washing results (dE AW - dE washed)

Example 3

Example 1 was repeated, in the compositions with additives used according to the invention (Mll to M15) instead of Celluzyme®, activity-equivalent amounts of cellulase BCE 103 (as described in WO 96/34108) were used and the washing tests were carried out under otherwise identical conditions in one Washing machine Miele® W918. From the washing results given in Table 3, the superiority of the cleaning performance of the agents according to the invention can also be seen here. Table 3: Washing results (dE AW - dE washed)

Claims

claims 1. Use of cellulase to increase the cleaning performance of textile detergents against polysaccharide stains. 2. Use of a combination of cellulase and amylase to increase the cleaning performance of laundry detergents against polysaccharide stains. 3. Use according to claim 1 or 2, characterized in that such amounts of cellulase are used that the agent has cellulolytic activities in the range from 10 mU / g to 700 mU / g, in particular from 25 mU / g to 400 mU / g . 4. Use according to claim 2 or 3, characterized in that such amounts of amylase are used that the agent has an amylolytic activity in the range from 10 U / g to 150 U / g, in particular from 15 U / g to 120 U / g having. 5. Use according to one of claims 2 to 4, characterized in that the ratio of cellulase to amylase activity is in the range from 1: 11500 to 1:15, in particular 1:4500 to 1:40. 6. Use of cellulase to remove polysaccharide stains on textiles. 7. A method for removing polysaccharide stains from textiles, characterized in that cellulase is used. 8. The method according to claim 7, characterized in that cellulase is used as a component of an aqueous cleaning solution, which may additionally contain the usual ingredients of wash liquors. 9. The method according to claim 8, characterized in that the aqueous cleaning solution has a cellulolytic activity in the range from 0.05 U / 1 to 2.5 U / 1, in particular from 0.1 U / 1 to 1.5 U / 1 .