EP1224254B1 - Enzymatic graying inhibitor - Google Patents

Description

The invention relates to a specific enzymatic graying inhibitor for use in detergents containing surfactants and detergents and / or cleaning agents which contain the specific enzymatic graying inhibitor in combination with other specially selected ingredients.

Today, detergents and cleaning agents use finely divided zeolite, in particular zeolite NaA, to bind the hardening agents, especially calcium and / or magnesium ions, in the washing water and dirt. So-called cobuilders or cobuilder systems are used to a considerable extent, particularly in the context of textile detergents, in particular to counteract undesirable incrustations.

These incrustations are deposits on the inner walls of washing machines and especially on laundry, such as call soap or organic residues. Such incrustations can adversely affect the feel, appearance, smell and absorbency of the laundry. The incrustations are particularly noticeable after repeated washing.

The graying of the laundry also usually only occurs after frequent washing, in particular when the washing solution's dirt-carrying capacity is insufficient due to insufficient detergent dosing and the dirt detached from the laundry is redeposed on the laundry.

In order to avoid incrustations and graying of the laundry or to keep them as low as possible, the above-mentioned builders or cobuilders are added to the detergents. The additional use of complexing agents, to which salts of aminocarboxylic acids such as nitrilotriacetic acid and phosphonic acid derivatives belong is known. Cobuilder combinations of this type counteract the precipitation of poorly soluble calcium salts and thus the incrustations caused on the textile or other surfaces when detergents and cleaning agents are used. Furthermore, detergents in particular can also contain additional graying inhibitors which are intended to counteract the redeposition of dirt particles suspended in the wash liquor on the washed textiles.

German published patent application DE 33 29 400 proposes using a mixture of methyl cellulose, carboxymethyl cellulose and copolymers of (meth) acrylic acid and maleic acid in a mixing ratio of 1: 1.5 to 4: 3 to 10 as an anti-graying additive in zeolite-containing detergents , where the cellulose ethers must have certain degrees of substitution.

European patent application EP - 054 325 describes the use of ternary mixtures of sodium carboxymethyl cellulose, a linear polycarboxylate and C _1-3 alkyl cellulose with degrees of substitution of at least 0.5 and degrees of polymerization up to 300 in detergents to inhibit graying.

In German published patent application DE-A-43 25 882 and DE-A-195 20 101 it is proposed to use cellulase as a graying inhibitor in washing or cleaning agents.

Although the measures described in the cited documents show satisfactory results in most cases, there is still a need to develop more effective graying inhibitor systems.

Surprisingly, it has now been found that the use of a very specific cellulase brings about a particularly good reduction in the redeposition of dirt particles on the washed laundry (redeposition) and graying.

The present invention relates to the use of Melanocarpus sp. or Myriococcum sp. Available 20K cellulase as a graying inhibitor in detergents and cleaning agents. Another object of the invention is the corresponding Use in detergents or cleaning agents which contain finely divided water-insoluble inorganic builders, in particular zeolite.

Further objects of the invention are detergents or cleaning agents which the Melanocarpus sp. or Myriococcum sp. 20K cellulase available in combination with an optionally genetically modified protease from Bacillus lentus and / or alkali percarbonate. When such combinations are used, the graying-inhibiting effect of the cellulase to be used according to the invention is increased still further.

The from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase is known from international patent application WO 97/14804. As described there, it has a molecular weight of about 20 kDa and has at least 80% of its maximum activity at 50 ° C. in the pH range from 4 to 9, with almost 50% of the maximum activity remaining at pH 10. As also described there, it can be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants. Cellulases which have a homology of over 80% to 20K cellulase can also be used for the purposes of the present invention.

A particular further advantage of the cellulase to be used according to the invention is that, when used, there is by far less loss in the wet tensile strength of washed textiles than when using other cellulases, although their color-refreshing and fabric-softening effect is not inferior to that of other cellulases.

K20 cellulase is preferably used in amounts such that a finished agent has a cellulolytic activity of 1 NCU / g to 500 NCU / g (can be determined by the hydrolysis of 1% by weight carboxymethyl cellulose at 50 ° C. and neutral pH and determination of the reducing substances released in the process Sugar using dinitrosalicylic acid, as described by MJBailey et al. In Enzyme Microb.Technol. 3: 153 (1981); 1 NCU defines the amount of enzyme that produces reducing sugars in an amount corresponding to 1 nmol glucose per second), especially 2 NCU / g to 400 NCU / g and particularly preferably from 6 NCU / g to 200 NCU / g. In addition, the agent may optionally contain other cellulases.

An agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of cellulolytic protein per gram of the total agent. The protein concentration can be determined using known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).

The protease from Bacillus lentus is stable and active under strongly alkaline conditions; it can be produced as described in the international patent application WO 91/02792 in Bacillus lentus (DSM 5483). This Bacillus lentus alkaline protease (BLAP) can be obtained by fermentation of the Bacillus licheniformis which has been transformed with an expression plasmid which carries the gene for BLAP under the control of the Bacillus licheniformis ATCC 53926 promoter. The composition as well as the spatial structure of BLAP is known (DW Godette et al., J. Mol. Biol. 228 , 580-595, 1992). This protease is characterized by the sequence of 269 amino acids described in the cited literature, a calculated molecular weight of 26,823 daltons and a theoretical isoelectric point of 9.7. Variants of this Bacillus lentus DSM 5483 protease accessible by mutation are described in US Pat. No. 5,340,735. Among these are protease enzymes which, in particular when washing textiles made of proteinogenic fibers, for example textile fabrics made of natural silk or wool, result in particularly low substance damage or destruction of the fiber dressings without loss of cleaning performance.

The proteases which can be used according to the invention include, in addition to the naturally occurring protease from Bacillus lentus, also genetically modified proteases of the abovementioned BLAP type, in which the amino acid leucine (L in customary) present at position 211 (BLAP count) in the wild-type protease at this point One-letter code) is replaced by aspartic acid (D) or glutamic acid (E) (L211D or L211E). These can be as in the international patent application WO 95/23221 can be produced. Instead or in addition, further changes to the original Bacillus lentus protease, such as at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I, may have been made. It is particularly preferred to use a variant in which at least one of the amino acid exchanges S3T, V4I, V193M, V199I, or L211D has been carried out. In the protease nomenclature on the exchange of individual amino acids described above, it should be noted that the numbering of the amino acid positions in BLAP differs from that which is frequently found for subtilisin BPN '. The numbering of positions 1 to 35 is identical in subtilisin BPN' and BLAP; due to the lack of corresponding amino acids, positions 36 to 54 in BLAP correspond to positions 37 to 55 in BPN ', likewise positions 55 to 160 in BLAP correspond to positions 57 to 162 in BPN' and positions 161 to 269 correspond to those from 167 to 275 in BPN '.

An agent according to the invention preferably has a proteolytic activity in the range from about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. The protease activity is determined according to the standardized method described below, as described in Tenside 7 (1970), 125: A solution containing 12 g / l casein and 30 mM sodium tripolyphosphate in water of 15 ° dH hardness (containing 0.058% by weight CaCl ₂ ^· 2 H ₂ O, 0.028 wt .-% MgCl ₂ ^· 6H ₂ O and 0.042 wt .-% NaHCO ₃₎ is heated to 70 ° C, the pH is by the addition of 0.1 N NaOH 8.5 set at 50 ° C. 200 ml of a solution of the enzyme to be tested in 2% by weight sodium tripolyphosphate buffer solution (pH 8.5) are added to 600 ml of the substrate solution. The reaction mixture is incubated at 50 ° C for 15 minutes. The reaction is then stopped by adding 500 ml of TCA solution (0.44 M trichloroacetic acid and 0.22 M sodium acetate in 3% by volume acetic acid) and cooling (ice bath at 0 ° C., 15 minutes). The TCA-insoluble protein is centrifuged removed, 900 ml of the supernatant are diluted with 300 ml of 2N NaOH. The absorption of this solution at 290 nm is determined with the aid of an absorption spectrometer, the zero absorption value being obtained by measuring a centrifuged solution, which is prepared by mixing 600 ml of the above-mentioned TCA solution with 600 ml of the above-mentioned substrate solution and then adding the enzyme solution determine. The proteolytic activity of a protease solution, which causes an absorption of 0.500 OD under the specified measurement conditions, is defined as 10 PE (protease units) per ml. In the agent according to the invention, the ratio of the cellulolytic activity, expressed in NCU / g, to the proteolytic activity, expressed in PE / g, is preferably 1:10 000 to 5: 1, in particular 1: 1600 to 4: 3.

The enzymes can, in particular for use in particulate compositions, as described for example in European patent EP 0 564 476 or in international patent application WO 94/23005 for other enzymes, be adsorbed on carriers and / or be embedded in coating substances in order to prevent them from occurring prematurely Protect inactivation. The combination of certain cellulase and optionally genetically modified protease, which is essential to the invention, can be achieved by incorporating the two separate enzymes or, in a known manner, separately assembled enzymes, or by cellulase and protease assembled together in a granulate, such as from international patent applications WO 96/00772 or WO 96 / Known 00773 can be used in agents according to the invention.

An agent according to the invention preferably contains up to 50% by weight, in particular 5% by weight to 30% by weight, of alkali percarbonate, sodium percarbonate being particularly preferred. It can be prepared according to known processes and, if desired, in particular for use in particulate compositions, if required, made up in granular form or stabilized and / or coated, as described, for example, in international patent applications WO 91/15423, WO 92/17400, WO 92/17404, WO 93/04159, WO 93/04982, WO 93/20007, WO 94/03553, WO 94/05594, WO 94/14701, WO 94/14702, WO 94/24044, WO 95/02555, WO 95/02672, WO 95/06615, WO 95/15291 or WO 95/15292 or the European patent applications EP 0 459 625, EP 0 487 256, EP 0 567 140, EP 0 623 553, EP 0 592 969 or EP 0 748 764. For reasons of stability, it is preferably used in the form of granules which, with the aid of alkaline earth metal sulfate, alkali metal sulfate, alkali metal silicate, alkaline earth metal halide, alkali metal halide, alkali metal carbonate, alkali metal hydrogen carbonate, alkali metal phosphate, alkali metal borate, alkali metal perborate, boric acid, partially hydrated aluminosilicate acids, carboxylic acids, carboxylic acids, carboxylic acids, carboxylic acids - And / or dicarboxylic acids, or mixtures of these was prepared or is enveloped. In a preferred embodiment, it has a morphology index (MI), as defined in EP 0 451 893, of less than 0.06.

In a preferred embodiment, the ratio of cellulase to be used according to the invention to alkali percarbonate is in the range from 0.0001 mg to 0.1 mg, in particular from 0.001 mg to 0.01 mg, of cellulolytic protein per% by weight of alkali percarbonate in the detergent or cleaning agent.

The detergents or cleaning agents can preferably be heavy-duty or mild detergents used in textile washing and, if appropriate, fabric softener that can be used in a rinse cycle after washing. In a preferred embodiment of the present invention, the use of the special cellulase relates to the reduction of the redeposition in textile washing with textile detergents based on finely divided water-insoluble inorganic builder components, in particular zeolite NaA.

The cellulase as well as the optionally additionally used enzymes, to which, in addition to the protease mentioned, in particular amylase, lipase, oxidase, peroxidase, cutinase, pullulanase, xylanase and / or hemicellulase and optionally further cellulases and / or proteases are to be counted and which are preferably in amounts from 0.1% by weight to 2% by weight are present in the form of liquid formulations, optionally with the addition of stabilizers, in particulate detergents, but preferably in the form of adsorbed onto carrier substances, embedded in coating substances or in the form of conventional granules inorganic and / or organic carrier materials, as described, for example, in German patent specification DE 16 17 232, German patent application DT 20 32 766 or DE 40 41 752 or European patent applications EP 168 526, EP 170 360, EP 270 608 or EP 304 331 , are used. The enzymes can be contained in separate particles or in the form of a multi-enzyme granulate, such as, for example, in German patent applications DE 44 22 433 or DE 44 22 609 or international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein the technology described, are used.

The washing and cleaning agents according to the invention, which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can, in addition to the combination used according to the invention, in principle contain all known ingredients which are customary in such agents. The agents according to the invention can in particular builder substances, surface-active surfactants, bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators as well as further bleaching agents based on organic and / or inorganic peroxygen compounds and further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators , Silver corrosion inhibitors and dyes and fragrances.

The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C ₁₂ -C ₁₈ monoolefins having an end or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -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 are produced by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 ° C -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, can be present in small amounts, preferably in amounts not above about 2 to 3% by weight. 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 as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol glycerol be preserved. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which. contain a synthetic, petrochemical-based straight-chain alkyl radical that has a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ 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 ₂₁ alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO. Because of their high foaming behavior, they are normally used in detergents only in relatively small amounts, 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 to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which are non-ionic surfactants. Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. Likewise, it is also possible to use alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants. 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 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 alkenyl succinic 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 also 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.

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-alkylamines, 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 alkylphenols having 5 to 12 carbon atoms in the alkyl radical are also useful.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols, preferably having 8 to 18 carbon atoms and average 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol, in which the alcohol radical may be methyl-branched linearly or preferably in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat 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 ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ 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 ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ 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. Extremely low-foaming compounds are usually used in particular in cleaning agents for use in machine dishwashing processes. These preferably include C ₁₂ -C ₁₈ alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, it is also possible to use other known low-foaming nonionic surfactants, such as, for example, C ₁₂ -C ₁₈ alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and also end-capped alkyl polyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European patent application EP 0 300 305, so-called hydroxy mixed ethers. 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 specifies the distribution of monoglycosides and oligoglycosides, is an arbitrary number, and the quantity to be determined analytically as well can 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 ¹ 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:

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) in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 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 oxyalkyl radical having 1 to 8 carbon atoms, C ₁ -C ₄ alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical, the alkyl chain thereof is substituted with at least two hydroxyl groups, or is alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical. [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 preferred non-ionic surfactants, the 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 produced by the method described in international patent application WO 90/13533. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-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 of the ethoxylated fatty alcohols, in particular 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 usually separated from one another by a so-called "spacer". This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized 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" but also "trimeric" surfactants. Suitable gemini 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 dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized 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, such as those used in international markets, can also be used Patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can be described.

Surfactants are present in detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, whereas agents for cleaning hard surfaces, in particular for machine cleaning of dishes , have lower surfactant contents of up to 10% by weight, in particular up to 5% by weight and preferably in the range from 0.5% by weight to 3% by weight.

An agent 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, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid and ethylenediaminephosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of the European patent EP 0 625 992 or the international patent application WO 92/18542 or the European patent EP 0 232 202 accessible by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids , Maleic acids and copolymers of these, which also contain small amounts of polymerizable substances in copolymerized form without carboxylic acid functionality can. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. 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 that have two unsaturated monomers can also be used as water-soluble organic builder substances Acids and / or their salts and, as a third monomer, vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate. 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 patent DE 42 21 381 and German patent application DE 43 00 772, and generally have a relative molecular weight between 1,000 and 200,000. Further 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, in particular for the production of liquid agents, can be used 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 paste-like or liquid, in particular water-containing, agents according to the invention.

Particularly suitable water-soluble inorganic builder materials are alkali silicates, alkali carbonates and alkali phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts. As water-insoluble, water-dispersible inorganic build materials In particular, crystalline or amorphous alkali alumosilicates are used 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. 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. Your calcium binding capacity. that 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 alumosilicate 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 in the agents according to the invention 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, especially 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 produced by the process of European patent application EP 0 425 427. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _{2x + 1} ^.yH ₂ O, in which x, the so-called modulus, a number of 1, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates. 9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and are preferred values for x 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 in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ ^.yH ₂ O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. δ-sodium silicates with a module between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/23 8 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the general formula mentioned above, in which x is a number from 1.9 to 2.1, are also prepared from amorphous alkali silicates. producible as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, 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 0 436 835. 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. Crystalline layered silicates corresponding to the above formula (I) are sold by the company. Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ ^· xH ₂ O, kenyaite), Na -SKS-2 (Na ₂ Si ₁₄ O ₂₉ ^· xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ ^.xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ ^· xH ₂ O, makatite). Of these, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ) are particularly suitable ^· H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ ^· 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline layered silicates is given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33 - 38 and in "Soap-oil-fat waxes, 116 year, No. 20/1990" on pages 805 - 808 published articles. In a preferred embodiment of agents according to the invention, a granular compound composed of crystalline layered silicate and citrate, of crystalline layered silicate and the (co) polymeric polycarboxylic acid mentioned above, as described for example in German patent application DE 198 19 187, or of alkali silicate and alkali carbonate such as is described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15.

Builder substances can optionally be present in the agents according to the invention in amounts of up to 90% by weight. They are preferably in amounts up to 75% by weight. contain. Detergents according to the invention have builder contents of in particular 5% by weight to 50% by weight. In agents according to the invention for cleaning hard surfaces, in particular for machine cleaning of dishes, the builder substance content is in particular 5% by weight to 88% by weight, with such agents preferably not using water-insoluble builder materials. In a preferred embodiment of agents according to the invention for in particular machine cleaning of dishes, 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali metal citrate, 5% by weight to 15% by weight of alkali metal carbonate and 20% by weight to Contain 40 wt .-% alkali disilicate.

Suitable peroxygen compounds for use in agents according to the invention include, in addition to the alkali percarbonate already mentioned, 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 conditions, to which perborates, persilicate and / or include persulfates such as caroate. 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. If an agent 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, and 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. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated 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, are preferred Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic acid trihydric anhydride. 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-benzoyicaprolactan, the WO 94 94/28102, 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 can be present in the customary quantitative range, preferably in amounts of 0.5% by weight to 10% by weight, in particular 1% 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 organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, in addition to water include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and those derived from the classes of compounds mentioned Ether. Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

In addition, the detergents can contain other constituents customary in washing and cleaning agents. These optional components include, in particular, enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners as well as colorants and fragrances. In order to provide silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. A cleaning agent for hard surfaces according to the invention can moreover have abrasive components, in particular from the group comprising quartz flours, wood flours. Plastic flours, chalks and micro glass balls and their mixtures. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.

To set a desired pH value which does not result from the mixture of the other components, the agents according to the invention 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 contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

The color transfer inhibitors which are suitable for use in textile detergents according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

Additional graying inhibitors can also be present in the agents according to the invention. 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. Water-soluble polyamides containing acidic groups are also 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 composition, are preferably used.

Textile detergents according to the invention 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 compounds of similar structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, an 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). Mixtures of the aforementioned optical brighteners can also be used.

In particular when used in machine 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 ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of various 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 compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, the enzymes and any further thermally sensitive ingredients, such as bleaching agents, optionally being added separately later. For the preparation of agents according to the invention with increased bulk density, in particular in the range from 650 g / l to 950 g / l, a method known from European patent EP 0 486 592 and having an extrusion step is preferred. A further preferred production using a granulation process is described in European patent EP 0 642 576.

For the preparation of agents according to the invention in tablet form, which can consist of one or more phases, of one color or of more than one color and in particular of one layer or of several, in particular of two layers, the procedure is preferably such that all constituents - if appropriate one layer each - are combined in one Mixer mixed together and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN. In the case of multi-layer tablets in particular, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at press forces between 5 and 20 kN, in particular at 10 to 15 kN. In this way, break-resistant tablets, which nevertheless dissolve sufficiently quickly under use conditions, are obtained with breaking and bending strengths of normally 100 to 200 N, but preferably over 150 N. A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The three-dimensional shape of the tablets is arbitrary and can be round, oval or angular, intermediate forms also being possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of angular or cuboid tablets, which are mainly introduced via the metering device, for example the dishwasher, depends on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular 26x36 mm or 24x38 mm.

Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

Examples example 1

The cellulases listed in Table 1 were added to an enzyme-free basic detergent BW1 . The cellulases were used in an amount based on protein that corresponded to an amount of 0.6 wt.% Celluzyme® 0.7T (manufacturer: Novo Nordisk) in the detergent used in each case. The tissue graying - determined by the reflectance after 10 washes - was determined, washing tests being carried out under the following conditions:
Washing machine: Miele® W918
Temperature: 40 ° C
Detergent dosage: 76 g
Water hardness: 16 ° dH
Load: 2.5 kg of clean laundry (cotton test fabric from the Krefeld laundry research institute, pillow cases, terry towels, undershirts and kitchen towels)
Soiling: 5 strands of cotton with standardized dust / skin fat soiling were added to each wash

The numerical values for the graying (given as% remission, average values for all textiles) after washing with the specified recipes are summarized in Table 1 below, whereby the initial remission value before the washes and the value for the enzyme-free basic detergent are also given for comparison , Table 1 medium graying initial value 87.3 BW1 54.5 BW1 + DAC ^a) 69.2 BW1 + Carezyme® (manufacturer. Novo Nordisk) 59.5 BW1 + 20K cellulase 73.0

a) cellulase according to WO 96/34108

It can be seen that when the cellulase to be used according to the invention is used, there is better inhibition of graying than when other celluases are used.

Example 2

Example 1 was repeated, in a departure from the procedure described there, 11 washes and a basic detergent BW2 was used which, in contrast to BW1, 1.2% by weight of an enzyme granulate containing the protease BLAP with an activity of 200,000 PE / g contained. Table 1 medium graying initial value 87.0 BW2 54.2 BW2 + DAC ^a) 73.1 BW1 + 20K cellulase 75.4

a) cellulase according to WO 96/34108

It can be seen that an agent according to the invention has a better graying-inhibiting effect than an agent which contains a different celluase instead of the cellulase to be used according to the invention.

Claims (10)

1. The use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto as a redeposition inhibitor in detergents.
2. The use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto as a redeposition inhibitor in detergents containing fine-particle water-insoluble inorganic builders, particularly zeolite.
3. The use of 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto for reducing redeposition in the washing of laundry with laundry detergents based on fine-particle water-insoluble inorganic builder components.
4. The use claimed in any of claims 1 to3, characterized in that the detergent contains as builder 10% by weight to 50% by weight and more particularly 10% by weight to 40% by weight of water-insoluble, water-dispersible detergent-quality inorganic builder material, more particularly crystalline alkali metal silicate, crystalline and/or amorphous alkali metal alumosilicate, more particularly zeolite A, zeolite P and/or zeolite X.
5. A detergent containing the 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or a cellulase more than 80% homologous thereto in combination with an optionally genetically modified protease from Bacillus lentus and/or alkali metal percarbonate.
6. A detergent as claimed in claim 5, characterized in that it has a cellulolytic activity attributable to the 20K cellulase obtainable from Melanocarpus sp. or Myriococcum sp. or to a cellulase more than 80% homologous thereto of 1 NCU/g to 500 NCU/g and more particularly 5 NCU/g to 400 NCU/g.
7. A detergent as claimed in claim 5 or 6, characterized in that at least one of the amino acid exchanges S3T, V4I, V193M, V199I or L211D has made in the genetically modified protease from Bacillus lentus.
8. A detergent as claimed in any of claims 5 to 7, characterized in that the ratio of cellulolytic activity expressed in NCU/g to proteolytic activity expressed in PU/g is preferably 1:10,000 to 5:1 and more particularly 1 : 600 to 4:3.
9. A detergent as claimed in any of claims 5 to 8, characterized in that it contains 50% by weight and more particularly 5% by weight to 30% by weight of alkali metal percarbonate, more particularly sodium percarbonate.
10. A detergent as claimed in any of claims 5 to 9, characterized in that it contains 0.0001 mg to 0.1 mg and more particularly 0.001 mg to 0.01 mg of cellulolytic protein per % by weight of alkali metal percarbonate.